Synthesis, Isolation and Purification of Esters in a Direct Esterification

Reaction Chemistry Tutorial

Key Concepts

 Esters have the general formula :

O
     
||
R - C - O - R'

 in which R and R' represent alkyl groups(1) and the functional group is the

-CO-O- group.
 Esters (alkyl alkanoates) can be synthesized or prepared by reacting an alkanol with
an alkanoic acid in the presence of an acid catalyst(2):

H+
alkanol + alkanoic acid
  →   alkyl alkanoate (ester)   +   water
 
H+
R'-O-H + HO-OC-R
  →   R'-OOC-R (ester) + H2O

 Fischer Esterification is the name given to the acid-catalysed reaction between an

alkanoic acid (carboxylic acid) and an alkanol (alcohol)(3).
 Synthesis or preparation of esters in the laboratory involves 3 steps:

Step 1: Synthesis of the ester

Step 2: Isolation of the ester

Step 3: Purification of the ester

 Esters of the low molar mass alkanoic acids and alkanols have fragrant, fruity
odours, and are used in perfumes and artificial flavourings.

Esters are also used as solvents.

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Synthesis of an Ester in the Laboratory Using Fischer Esterification

An ester can be synthesised in the laboratory by heating a reaction mixture consisting of the
alkanol (alcohol), the alkanoic acid (caboxylic acid) and a small amount of concentrated sulfuric
acid catalyst in a vessel fitted with a water-cooled condenser (Liebig condenser) to prevent loss
of volatile material.
The steps in the procedure for the synthesis of the ester ethyl acetate (ethyl ethanoate) are given
below:

1. Add 15 mL of alcohol (eg, ethanol) and 10 mL carboxylic acid (eg, glacial acetic acid), to
a 50 mL round bottom flask.
2. Slowly add about 1 mL of concentrated sulfuric acid and a few boiling chips which will
prevent "bumping"(4).
3. Assemble the glassware as shown in the diagram below:

4. Turn on the heating mantle to achieve a gently boiling of the reaction mixture.
5. Reflux the mixture for 30 minutes.
6. Turn off the heat and allow the mixture to cool. 
Note: your round bottom flask now contains some ester (the desired product), as well as
water, unreacted alcohol, unreacted carboxylic acid, and sulfuric acid.

Safety Considerations for the synthesis of esters:

 Alcohols are flammable, keep clear of flames.

 Liquid carboxylic acids are corrosive, avoid skin contact.
 Concentrated sulfuric acid is corrosive, avoid skin contact.

Improving the Yield of Ester Prepared by Fischer Esterification

The esterification reaction is reversible, reactants are in equilibrium with products as shown in
the chemical equations below:

  reactants   products
alkyl alkonoate
general word equation: alkanol + alkanoic acid ⇋ + water
(ester)
examples: acetic acid ethyl acetate
ethanol + ⇋ + water
(ethanoic acid) (ethyl ethanoate)
propan-1-ol + acetic acid ⇋ propyl acetate + water
 (1-propanol) (ethanoic acid) (propyl ethanoate)
butan-1-ol acetic acid butyl acetate
+ ⇋ + water
(1-butanol) (ethanoic acid) (butyl ethanoate)

When the reaction reaches equilibrium there is still a large amount of reactants left in the mixture
resulting in a poor yield of the ester.

The yield of ester can be improved by increasing the concentration of one of the reactants (either
the alcohol or the carboxylic acid). 
By Le Chatelier's Principle an excess of one reactant will drive the reaction to the right,
increasing the production of ester, and therefore increasing the yield of ester. 
In our experiment we are using an excess of carboxylic aicd (acetic acid which is also known as
ethanoic acid).

From the balanced chemical equation, you will also appreciate that the presence of water in the
reaction mixture will drive the equilibrium to the left, favouring the formation of reactants rather
than ester. 
So, another way to improve yield is to remove the water as it forms. 
Concentrated sulfuric acid can be used for this purpose because it reacts rapidly with water to
form a hydrated form of sulfuric acid, effectively removing the water from the reaction
mixture(5).

Increasing the Rate of the Direct Esterification Reaction

The esterification reaction is quite slow.

Heating the reaction mixture will speed up the rate of reaction. 

The experimental technique we are using is known as "heating under reflux". As the volatile
components in the reaction mixture vaporise, the hot vapours rise up into the condenser. Cool
water running around inside the water-jacket around the condenser removes the heat from the hot
vapours, cooling them down and allowing them to condense on the inside of the condenser. This
cooled liquid runs back down the inside of the condenser and is returned to the reaction mixture. 
Heating the reaction mixture under reflux prevents the loss of volatile reactants and products.

Concentrated sulfuric acid is used as a catalyst to speed up the rate at which the ester is
formed(6).

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Isolation of the Ester Produced by Direct Esterification

The ester we synthesised above is impure. 
The round bottom flask now contains a mixture of organic and inorganic substances as shown
below:

organic substances inorganic substances

ester  water 
(desired product) (undesired product of the reaction)

alcohol  sulfuric acid 

(excess reactant now present as an impurity) (used to catalyse the reaction)

carboxylic acid 
(excess reactant now present as an impurity)

These substances are all miscible with water, except the ester.

We will need to isolate the part of the mixture that contains the ester. 
We can do this by taking advantage of the ester's low solubility in water, and, the fact that the
ester will be less dense than water so it will float on top of a layer of water. 
We use a piece of glassware called a separating funnel to isolate the less dense ester layer from
the aqueous layer as described in the steps below:

1. With the stopcock closed, pour the cooled mixture

into a separating funnel containing about 20 mL of
water. 
Stopper the funnel and shake. 
Allow the layers to separate.
2. With the separating funnel suspended above a conical
fask (erlenmeyer flask) and the stopper removed,
open the stopcock and allow the more dense aqueous
layer to flow into the conical flask. 
Close the stopcock.
3. Repeat the process above by adding more water and
then separating the layers. 
This should remove most of the water soluble species
(that is the acids and the alcohol).
4. Add 5 mL sodium carbonate solution
to neutralise acid still present(7). 
Swirl the flask until the production of carbon dioxide
gas is no longer vigorous. 
Repeat this process until no more carbon dioxide gas
is produced.
5. Allow the mixture to stand so that it separates into
layers, then remove the denser aqueous layer by opening the stopcock. 
Close the stopcock once the aqueous layer has been run out.
 6. Wash the remaining organic layer with about 20 mL of water, stand to allow the layers to
separate, then open the stopcock once more to run out the aqueous layer. 
Close the stopcock once the aqueous layer has been removed.
7. Add a small amount of anhydrous magnesium sulfate to a clean, dry conical flask. 
Run the remaining organic contents of the separating funnel into the conical flask. 
Stopper the conical flask and allow to stand for 15 minutes.
8. Decant the contents of the conical flask into a clean, dry, 50 mL round bottom flask.

Initial washing with water will remove most of the water soluble species which includes any
excess alcohol (ethanol), carboxylic acid (acetic acid), and sulfuric acid. 
The ester is not very soluble in water so will separate into a separate layer. 
The ester is less dense than water so the ester layer floats on top of the aqueous layer. 
The density of water and ethyl acetate ester is given in the table below:

relative
substance density / g mL-1
density
water 1.0 more dense
ethyl acetate
0.9 less dense
(ethyl ethanoate)

After washing there will still be traces of acid left in the organic, ester, layer. 
An aqueous solution of sodium carbonate (or alternatively sodium hydrogen carbonate(8)) is used
to neutralise any remaining acid:

sodium carbonate + acid → water soluble salt + carbon dioxide gas + water

net equation: CO32-(aq) + 2H+(aq) → CO2(g) + H2O(l)

As sodium carbonate is added, bubbles of carbon dioxide form. When all the acid has been
neutralised, adding sodium carbonate will no longer produce bubbles of carbon dioxide gas. 
The final rinsing with water should remove traces of the water soluble salt formed.

Anhydrous magnesium sulfate is added to the remaining mixture because it is a "drying agent", it
will remove water from the mixture(9).

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Purification of the Ester

The organic layer we decanted into the round bottom flask contains our impure ester.
The ester can be purified by distillation because the various components possible in the mixture
have different boiling points.

The boiling points of the components which could still be in the mixture are given in the table
below:

boiling point / °C ester boiling point / °C

reactant  
(at 1 atm) (product) (at 1 atm)
ethyl acetate
water 100   77
(ethyl ethanoate)
acetic acid
118      
(ethanoic acid)
sulfuric acid 142      

The ester we have prepared, ethyl acetate (ethyl ethanoate) has the lowest boiling point of all the
possible components in the mixture. 
Therefore ethyl acetate will be the first fraction collected as the distillate. 
A sharp boiling point is an indication of the purity of the ester.

The procedure for the distillation of the mixture containing the ester is outlined below:

1. To the mixture in the round bottom flask as

prepared above, add boiling chips to prevent
"bumping".
2. Set up the distillation equipment as in the diagram
on the right. 
Notes: 
(i) the mixture in the round bottom flask is best
heated using a heating mantle, but an oil bath
could also be used. The method of heating is not
shown in the diagram. 
(ii) the reservoir (bulb) of the thermometer needs
to be level with the intake to the condenser to
ensure that the temperature being recorded is that
of the vapour that is being condensed in the
condenser, and not the temperature of the vapour
that is being condensed in the fractionating column and therefore returning to the mixture
in the round bottom flask.
3. Gently heat the mixture.
4. Collect the distillate in a clean, dry flask. 
Discard any distillate collected before the temperature of the vapour reaches a constant.
Do not discard the distillate that collects at a constant temperature that is approximately
the same as that expected for your ester. 
Replace the collection flask with another flask as soon as you think the temperature of the
vapour is increasing, and stop heating the mixture.
 5. Do not continue heating the mixture to dryness. 
There should always be some mixture left in the flask when you turn off the heat.

Note the appearance of your purified ester. If it looks cloudy there is probably water present.

Note the smell of your ester by using your hand to gently waft ester vapour to your nose. 
NEVER place you face directly over the flask to note the odour!

Note that the fraction that you collect will depend on the relative boiling points of the
components in the mixture. 
If you have not prepared ethyl acetate, the boiling point of the ester will not be 77°C 
The table below gives the approximate boiling points of some other acetate esters that you could
synthesise in the laboratory:

methyl acetate ethyl acetate propyl acetate

butyl acetate
ester (methyl (ethyl (propyl
(butyl ethaoate)
ethanoate) ethanoate) ethanoate)
boiling point
56 77 101 124
°C

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Examples of Esters

The name of an ester produced by direct (Fischer) esterification can tell us how the ester has
been produced.

The first part of the name comes from the name of the alkanol used, with the suffix "anol"
replaced by the suffix "yl".

alkanol becomes alkyl
The second part of the name comes from the name of the alkanoic acid used, with the suffix "oic
acid" replaced by the suffix "oate".

alkanoic acid becomes alkanoate

Name of the ester is two separate words: alkyl alkanoate

Some examples of the synthesis of different esters, their names and usefulness, is given in the
table below:

reactants   products use

H
carboxylic wat
alcohol + +
+ ester
acid er
⇋
acetic acid H+ methyl acetate
methanol + water + solvent
(ethanoic acid) ⇋ (methyl ethanoate)
H O H H O H
                   
| || | H+ | || |
H- C -O- H + HO- C - C -H H2O + H- C -O- C - C -H
| | ⇋ | |
                       
H H H H

H+ apple
methanol + butanoic acid water + methyl butanoate
⇋ flavour
O H H H
H           H O H H H
      || | | |            
| | || | | |
- H
+
HO
H- C -O- H + - C-C-C-CH H2O + H- C -O- C -C - C - C -H
| ⇋ | | | |
      | | |              
H             H H H H
H H H

formic acid H+ ethyl formate rum

ethanol + (methanoic water +
acid) ⇋ (ethyl methanoate) essence
H H H H O
        O        
| |     H+ | | ||
||
H- C - C -O- H + H2O + H- C - C -O- C -H
| |
HO- C -H ⇋ | |
                       
H H H H

acetic acid H+ ethyl acetate

ethanol + water + solvent
(ethanoic acid) ⇋ (ethyl ethanoate)
H H O H H H O H
                       
| | || | | | || |
H+
H- C - C -O- H + HO- C - C -H H2O + H- C - C -O- C - C -H
| | | ⇋ | | |
                           
H H H H H H

H+ pineappl
ethanol + butanoic acid water + ethyl butanoate e
⇋ flavour
 O H H H
H H           H H O H H H
        || | | |              
| | | | || | | |
- H
+
HO
H- C - C -O- H + - C-C-C-CH H2O + H- C - C -O- C - C - C - C -H
| | ⇋ | | | | |
        | | |                
H H             H H H H H
H H H

pentan-1-ol acetic acid H+ pentyl acetate banana

+ water +
(1-pentanol) (ethanoic acid) ⇋ (pentyl ethanoate) flavour
H H H H H O H H H H H H O H
                                   
| | | | | || | H+ | | | | | || |
H- C - C - C - C - C -O- H + HO- C - C -H H2O + H- C - C - C - C - C -O- C - C -H
| | | | | | ⇋ | | | | | |
                                       
H H H H H H H H H H H H

pentan-1-ol H+ apricot
+ butanoic acid water + pentyl butanoate
(1-pentanol) ⇋ flavour
O H H H H H H H H O H H H
H H H H H                              
              || | | | | | | | | || | | |
| | | | |
- H
+
HO - -
H- C - C - C - C - C -O- H + - C-C-C-CH H2O + H- C - C - C - C - C O- C - C - C - C
| | | | | ⇋ H
              | | | | | | | | | | |
H H H H H                                  
H H H H H H H H H H H

octan-1-ol H+ orange
+ butanoic acid water + octyl butanoate
(1-octanol) ⇋ flavour
H H H H H H H H
                    O H H H
| | | | | | | |            
H H H H H H H H
               
O H H H
       
|| | | | | | | | | | | | || | | |
-
- H+ - -
H- C - C - C - C - C - C - C - C O H + HO- C - C - C - C H2O + H- C - C - C - C - C - C - C - C C- C- C - C
-
| | |
H
⇋  
|
 
|
 
|
 
|
 
|
 
|
 
|
 
|
O-
     
|
 
|
 
|
H
 
| | | | | | | |             H H H H H H H H H H H
                    H H H
H H H H H H H H

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Footnotes:

(1) For this tutorial, we will only be concerned with examples where R is an alkyl group (that is a group derived from the alkane series). 
And, we only be dealing with esters derived from straight chain carboxylic acids, so the name of the ester will be two words. 
It should be noted that the names of more complex esters will be made up of more than 2 words. 
If more than organyl group (alkyl, aryl etc) is present, they are cited in alphabetical order.

(2) During the esterification reaction, the C-O bond in the carboxylic acid is broken. 
Evidence for this comes from experiments using isotopically labeled reactants. 
If some of the alcohol used contains the  18O isotope, the atoms of this isotope are all found in the ester product and NOT in the water.

(3) There are other ways to produce esters besides the direct (Fischer) esterfication of a carboxylic acid with an alcohol. 
(a) Alcoholysis of acid chlorides, anhydrides, or nitriles, produces esters. 
(b) Reaction of the salt of a carboxylic acid with an  alkyl halide or sulfate will produce an ester. 
(c) Trans-esterification of an ester produces a new ester.

(4) If a liquid is largely free of air, and the glass flask is clean and very smooth, the liquid may superheat, a condition in which the temperature
of the liquid rises above its boiling point. 
In a superheated liquid it is hard to form vapour bubbles resulting in irregular expulsion of bubbles of vapour, or, bumping. 
Boiling chips (pieces of porous pot) provide an additional source of minute air bubbles which act as a nucleus for building bubbles of vapour in
the liquid, allowing the liquid to boil quietly.

(5) An even better way to improve ester yield is to use anhydrides in the synthesis instead of carboxylic acids. 
For example, the reaction between ethanol and acetic anhydride is irreversible, and goes to completion within minutes. 
acetic anhydride + ethanol → ethyl acetate + acetic acid

(6) Although sulfuric acid plays a vital role in the esterification reaction mechanism, it is beyond the scope of this tutorial. Suffice it to say that
since the sulfuric acid that is used during in the reaction is re-produced at the end of the reaction mechanism, sulfuric acid is acting as a catalyst
for the reaction.

(7) For a saturated sodium carbonate solution, dissolve 4.5 g sodium carbonate in 15 mL of distilled water.

(8) If you are an organic chemist you will name HO-CO-O-Na+ as sodium hydrogen carbonate, but if you are an inorganic chemist you will
probably name it sodium hydrogencarbonate. 
Another common name for the same compound is sodium bicarbonate.

(9) Anhydrous magnesium sulfate is used as a drying agent in preference to fused or "anhydrous" calcium chloride which can combine with some
esters. 
Note the use of the term "drying agent". No  chemical change  is involved in using a drying agent, the drying agent is used to remove
excess water molecules from the mixture. 
In a dehydration reaction, however, there is a chemical change. Atoms of hydrogen and oxygen are removed from reactant molecules and
produce water as product.