CAPE Chemistry – UNIT 2 – Chemical Principles and Applications II

Module 1 – The Chemistry of Carbon Compounds Lecture Notes 13

Ester
General Information
1. Are carboxylic acid derivatives
2. Contain the R-COO-R functional group
3. Have the general formula CnH2n + 1COO CxH2x + 1
4. Considered aromatic (sweet smelling) compounds.
Physical Properties
1. State at room temperature – The simple ester are liquids at room temperature and pressure. As the
esters become more complex, there is a change of state from liquid to solid. For instance, oils are
liquids at room temperature but fats (like butter) is a solid at room, both of which are esters.

2. Boiling point – Esters have higher boiling points than corresponding alkanes and alkenes of similar
size. Generally, as chain length increases, boiling point increases. Esters have similar boiling
points to aldehydes and ketones since that all contain the carbonyl carbon which allows for
permanent dipole-dipole forces to be established between molecules. However, esters have lower
boiling points than alcohols and carboxylic acids since esters do not hydrogen bond with
themselves.

3. Solubility – The simple esters are fairly soluble in water since the carbonyl oxygen can hydrogen
bond with water molecules. However, as chain length increases, solubility drastically decreases.
However, the larger esters are soluble in all proportions in organic solvents.

Preparation of Esters

Esters can be prepared in the lab by reacting either, a carboxylic acid and an alcohol (in the presence of a
catalyst) or an acyl chloride and an alcohol (occurs without a catalyst). For large esters, the acid and the
alcohol are heated under reflux in the presence of concentrated sulphuric acid as the catalyst. However,
the resulting mixture would have to be fractionally distilled in order to obtain the ester. On the other hand,
smaller esters can be made by reacting the acid and alcohol and simple distilling the mixture as the ester
is being form. The ester will have to lowest boiling point in the mixture can so will come off first. Further,
the reaction is reversible.

In the mechanism for the acid catalysed reaction of an acid and an alcohol, the carbonyl carbon is
protonated then the lone pair on the hydroxyl oxygen of the alcohol, attacks the partial positive carbonyl
carbon. This results in the breakage of the C=O double bond. The hydrogen on the attached alcohol then
transfer to the OH group on the original acid to form a better leaving group (a water molecule) which
leaves. The lone pair on the carbonyl oxygen then goes to reform the double bond and the attached
hydrogen is lost. This produces the ester, water and the catalyst is reformed. For instance, the mechanism
for the production of ethyl methanoate is:
Ethyl methanoate can be produced from an acyl chloride by the following mechanism.

Question: Write mechanisms for the production of (i) pentyl ethanoate and (ii) butyl propanoate from an
acid and an acyl chloride in each case.

Hydrolysis of Esters
When esters are formed, a condensation-elimination reaction occurs where a water molecule is produced.
Hydrolysing an ester under acidic conditions, reproduces the original acid and alcohol used to form the
ester. Further, the reaction is reversible. Since the reaction with water is too slow, the ester is usually
heated with dilute hydrochloric or sulphuric acid. In the mechanism for this reaction, the carbonyl oxygen
of the ester is protonated. The lone pair on a water molecule then attacks the partial positive carbonyl
carbon and adds unto the chain. A hydrogen from the added water molecule then transfers to the oxygen
of the ester linkage. The alcohol then leaves the molecule. The lone pair on the carbonyl oxygen then
reforms the double bond and the catalyst is reformed along with the carboxylic acid. For example, the
mechanism for the acid catalysed hydrolysis of ethyl methanoate is:

The mechanism for the acid catalysed hydrolysis of pentyl ethanoate is:

Esters may also be hydrolysed in the presence of an alkali such as sodium hydroxide solution. This method
is easier since it is not reversible and it is easier to separate the products once they are formed. The ester
is heated under reflux with dilute sodium hydroxide solution. In the base catalysed hydrolysis of an ester,
an alcohol and a salt of the carboxylic acid is formed.
Questions:
1. The equation below shows the acid hydrolysis of the ester ethyl ethanoate using an excess of dilute
hydrochloric (or sulphuric) acid.

a. The reaction doesn’t seem to include the hydrochloric or sulphuric acid. Why not?
b. Why is an excess of the acid used?
c. Write the formulae for the products if you hydrolysed methyl propanoate in the same way.

2. Esters are more usually hydrolysed by alkaline hydrolysis using sodium hydroxide solution.
a. Write the equation for the hydrolysis of methyl ethanoate using sodium hydroxide solution.
b. Briefly, how would you treat the reaction mixture in order to get a sample of each of the
alcohol and the carboxylic acid.
Saponification (Alkaline Hydrolysis)
Soaps are made from the base (alkaline) hydrolysis of fats and oils. They are the salts of a long chain fatty
acid. Fats are made up of a fatty acid and a glycerol molecule. Alkaline hydrolysis occurs in two steps.
First, the ester is hydrolysed to form the carboxylic acid and an alcohol. The base then reacts with the
carboxylic acid to from the salt of the acid (soap).

Sodium chloride is added to the final reaction mixture to wash the soap and remove excess base and
glycerol through a process known as salting out.

Transesterification
This is the process of reacting an ester with an alcohol to form another ester and an alcohol. The ester
produced from the transesterification is usually simpler and is more useful as a fuel since it has a lower
mass; hence its viscosity is lower and it burns more easily. This process requires heat and acids, alkalis or
alkoxides are commonly used as catalysts.
Biodiesel is the ethyl ester of a fatty acid made via tranesterification of waste vegetable oil using ethanol
and NaOH as the catalyst. In this process, all the water from the fat is removed. The sodium hydroxide
catalyst is then added to a large excess of ethanol and added to the fat and produces biodiesel. Biodiesel
is an example of a biofuel.