1.

Ester
Ester is an acyl group bonded to –OR or –OAr. A cycle ester is called a
lactone. Ester relegated by carboxylic acid. A carboxylic acid contain of –COOH
group, and an ester, its hydrogen changed by a hydrocarbon group of many kind
(Clark, 2007)
The ester group is an important functional group that can be synthesized
in a number of different ways. The low-molecular weight esters have very
pleasant odors and are indeed the major components and odor aspects of a
number of fruits. Although the natural flavor may contain nearly 100 different
compounds, singleesters approximate the natural odors and often used for food
industry for artificial flavors and fragrances. (Williamson, 1994).
Synthesizing esters :
1. Carboxylic acid and alcohol
O O

H2 H2 H2 H2 H2 H2
C C C C OH C C C C OCH2CH3

𝐻+
+ CH3CH2OH → +
H2O
2. Acid halides and alcohol
𝐻𝐶𝑙
Cl-CO-CH2-CO-Cl + 2(CH3)3COH → (CH3)3-COO-CH2-COOC-(CH3)3
3. Acid anhydride and alcohol or phenol
O
O CH3
H2
C O C C CH3
H

C OH

O + CH3CH2CH(OH)CH3  O

(Fessenden & Joan, 1986)

Commercial esters have been widely produced by industry. One of them
is the acetate ester of alcohol which is needed for various uses such as ethyl
butyl, isopropyl, and amyl acetate which are used as solvents for cellulose
nitrate. In the food and beverage industry, ethyl and butyl acetate are routinely
used as one of the components used to give flavor while the manufacture of
perfume is added isopropyl, benzyl, and methyl acetate as additives (Abraham,
2010).
 Esters are neutral organic compounds, do not react with metals Na and
PCl3. Esters consisting of low molecular weight acids and alcohol are colorless
liquid compounds, slightly soluble in water with fragrant odors, and volatile
(Fessenden & Joan, 1986).
2. Esterification Reaction
The esterification reaction with an acid catalyst is a reversible reaction
(Parlan, 2013). General reactions:

Figure 2. Esterification Reaction

Source : (Fessenden dan Fessenden,1982).
When achieving equilibrium, the quantity of carboxylic acid cannot be
ignored. By controlling the reaction conditions, and obtaining an ester in the
number of the alloys is offered, the equilibrium shifts to the right and thus the
more formed esters (Parlan, 2013).
Esterification is influenced by several factors including the molecular
structure of alcohol a process, and the concentration of catalysts and reactants
(Hart, 2003).
a. Reactivity of alcohol to esterification:
CH3OH> Primary> Secondary> Tertiary
b. Reactivity of carboxylic acids to esterification:
HCOOH> CH3COOH> RCH2COOH> R2CHCOOH> R3CCOOH
(Fessenden and Fessenden, 1982).
The rate of esterification reaction is strongly influenced by the molecular
structure of the reactants and radicals formed in the compound between the data
about the reaction rate and the mechanism arranged based on the character of the
kinetics, while the data about the reaction progress are expressed as equilibrium
constants. In general, the esterification reaction rate has the following properties:
1. Primary alcohol reacts most quickly, followed by secondary alcohol and
at the latest tertiary alcohol.
 2. Double bonds slow down the reaction.
3. Aromatic acid (benzoate and p-toluat) reacts slowly, but has a high
conversion limit.
4. The longer the alcohol chain, tends to accelerate the reaction or not too
much influence on the reaction rate (Harold, 1983).

Several types of esterification methods include:

a. How to Fischer
The most common method for preparing a catalyst is a carboxylic acid and
an alcohol, a process known as Fischer esterification. The reaction is reversible
and requires removal of water to drive it to completion. (Selfe, 2000)
This Fischer esterification reaction reaches equilibrium after a few hours
of refluxing. The position of the equilibrium can be shifted by adding more of
the acid or of the alcohol depending on cost or availability. The mechanism of
the reaction involves initial protonation of the carboxyl group, attack by the
nucleophilic hydroxyl group of the alcohol, a proton transfer, and loss of water,
followed by deprotonation to give the ester. Because each of these steps is
completely reversible, this process is also, in reverse, the mechanism for the
hydrolysis of an ester (McMurry, 2000).

Figure 1. Mechanisme Fischer Esterification Hydrolysis for an ester

Source : McMurry, 2000
The mechanism of the ficher esterification reaction consists of several steps:
1. Transfer of protons from an acid catalyst to the carbonol oxygen atom,
thereby increasing the nucleofility of the carbonyl atom.
2. The carbonyl carbon atom is then attacked by oxygen atoms from
alcohol, which are nucleophilic so that oxonium ions are formed.
3. The release of protons from the hydroxyl groups belonging to the alcohol
produces an activated complex.
 4. Protonation of one of the hydroxyl groups followed by the release of
water molecules produces esters (Hart, et al., 2003).

b. Esterification with acyl halides

Acyl halides are the most effective carboxylic acid derivatives. Acyl
chloride is cheaper than other acyl halides. Acyl halides are usually made from
acids with thionyl chloride or phosphorus pentachloride.

Figure 2. Reaction of esterification with acyl halide

Source : Bruice, 2014
c. Esterification between carboxylic acids with conjugated diene
Esterification by using carboxylic acids with conjugated dienes not
accompanied by oxygen with acid catalysts has also been widely developed.
The esterification results between the carboxylic acids with the most
commonly conjugated dienes are n-butyl acetate, 2-methyl-2-butyl butanoate,
cyclohexane-3-yl-benzoate and others (Bruice, 2014).

The factors that influence the esterification reaction include:

a. Reaction Time
The longer the reaction time the greater the likelihood of contact
between substances will result in large conversions. If the equilibrium of
the reaction has been reached then the increase in reaction time will not
be beneficial because it does not increase the yield.
b. Stirring
Stirring will increase the frequency of collisions between reacting
substance molecules with substances that react to accelerate the reaction
and the reaction occurs perfectly. In accordance with the Archenius
equation:
k = A e (-Ea / RT)
 where, T = absolute temperature (ºC)
R = general gas constant (cal / gmol ºK)
E = Activation force (cal / gmol)
A = collision factor (t-1)
k = reaction speed constant (t-1)
The greater the collision, the greater the price of the reaction speed
constant. So that in this case stirring is very important considering the
solution of oil-catalyst-methanol is an immiscible solution.
c. Catalyst
The catalyst serves to reduce the activation power in a reaction so
that at a certain temperature the constant price of the reaction speed is
greater. In the esterification reaction that has been carried out, it usually
uses a catalyst concentration between 1 - 4% by weight to 10% by weight
of the reactant mixture.
d. Reaction Temperature
The higher the temperature operated, the more conversions
produced, this is in accordance with the Archenius equation. When the
temperature rises, the price of k increases so that the reaction runs faster
and the results of the conversion get bigger. (Mc Ketta, 1978)
3. Reflux
Reflux is the separation of a component from a substance. Basically the
principle of reflux is the same as extraction. In this method all desired substances
will end in a solvent and all disturbing substances in another solvent (day and
underwood, 2002).
The principle of the reflux method is that volatile solvents used will
evaporate at high temperatures, but will be cooled with a condenser so that the
solvent that was in the form of steam will condense on the condenser and
descend again into the reaction container so the solvent will remain during the
reaction. While the N2 gas flow is given so that there is no water vapor or oxygen
gas that enters especially in organometallic compounds for the synthesis of
inorganic compounds because of its reactive nature (day and underwood, 2002).
Advantages and disadvantages of the Reflux method:
 1. Advantages of the Reflux method The advantage of this method is that it is
used to extract samples that have a rough texture and are resistant to direct
heating.
2. Loss of the Reflux method The disadvantage is that it requires a large total
volume of solvents and a number of manipulations from the operator (day and
underwood, 2002).
Reflux method procedure:
High temperature heating without any substance released. The condenser tube is
connected to a hose filled with cold water. The inlet hose is at the bottom and
the water hose comes out at the top. The working principle in this series of reflux
is four processes, namely:
1. Heating, occurs when the feed is heated in the boiling boil, evaporating
(evaporation) occurs when the feed reaches the boiling point and changes the
phase into steam which then enters the condenser inside
2. Evaporating
3. Condensation, this process occurs in the condenser, so there is a temperature
difference between the condenser inside which contains hot steam with an
outside condenser containing cold water, this causes a decrease in
temperature and phase changes from the steam to become liquid again and
4.Cooling, occurs in a bucket, in the bucket we put ice and water, so that when
we turn on the pump, cold water will flow from the bottom to the outside
condenser, the water must be flowed from the bottom of the condenser instead
of above so that there is no air turbulence blocking and so that the water is
fully filled (day and underwood, 2002)..
4. n-butyl
The n-butyl acetate compound is an ester of acetic acid and n-butanol. The
compound is made through an esterification reaction, and a strong acid catalyst.
For example concentrated H2SO4 (Tim Dosen Kimia Organik, 2016).
 Figure 3. n-butyl formation reaction
Source : Tim Dosen Kimia Organik, 2016
Physical properties and uses of n-butyl
The n-butyl acetate compound is an ester of acetic acid with n-butanol.
esters have distinctive physical properties, which give a fragrant aroma or smell,
some esters have the aroma of fruits such as bananas. but besides that esters can
also produce scents other than fruits (Fessenden and Fessenden, 1982).
The n-Butyl acetate is transparent liquid that is widely used as an organic
solvent, an extraction solvent and a dehydrant in industries. It is also used in
large quantities in the manufacture of coatings and other branches of chemical
industry. In spite of modern trends towards elimination of volatile solvents,
consumption of butyl acetate is expected to grow in near future because of its
lower impact on environment, compared to some other types of solvents. Owing
to its lower impact on environment, n-butyl acetate is able to replace the toxic
and teratogenic ethoxy ethyl acetate that is often used as a solvent (Giwa, 2012).

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