Alcohols, esters and carboxylic

acids
ALCOHOLS
Alcohols are organic molecules containing the hydroxyl group,
OH. With one hydroxyl group substituted into an alkane
molecule, the general formula is CnH2n + 1OH.
Reactions of the alcohols

1 Combustion

2 Substitution to form a halogenoalkane

Sulfur dichloride oxide, SOCl2, can also be used to substitute a
chlorine atom into an alcohol molecule, as shown below

We can also use phosphorus halides to provide the halogen

atoms for this substitution reaction.
3 Reaction with sodium metal

if the excess ethanol is evaporated off after the reaction, a

white crystalline solid is left. This is the sodium ethoxide.
4 Esterification

The first part of an ester’s name comes from the alcohol: in

this case ethanol, giving ‘ethyl …’. The second part comes
from the carboxylic acid, in this case ethanoic acid, giving ‘…
ethanoate’
Hydrolysis of esters

Esters can be hydrolysed by heating under reflux with either an

acid or a base. Refluxing with an acid simply reverses the
preparation of the ester from an alcohol and a carboxylic acid.
5 Dehydration

As the small molecule removed from the alcohol molecule is

H2O, this reaction is also known as dehydration.

For example:
6 Oxidation

1. Oxidation of a primary alcohol

The oxidising agent used is a solution of potassium

dichromate(VI), (K2Cr2O7) acidified with dilute sulfuric
acid. To make the aldehyde, the primary alcohol is heated
gently with acidified dichromate solution. The reaction
mixture turns green as the orange dichromate ions, Cr2O7
2–(aq), are reduced to green Cr3+(aq) ions.
 The formed aldehyde has
a lower boiling point than
the alcohol and can
therefore be distilled off
as soon as it forms.

If the aldehyde formed is not distilled off,

further refluxing with excess oxidising agent will oxidise
the aldehyde to a carboxylic acid
 2 Oxidation of a secondary alcohol

The oxidising agent used is a solution of potassium

dichromate(VI), acidified with dilute sulfuric acid.
To produce a ketone, this oxidising agent must be heated with a
secondary alcohol. The ketone formed cannot be further
oxidised, even if we reflux the reaction mixture and add excess
oxidising agent. Therefore we do not need to distil out the
ketone product immediately.
Given three unknown alcohols, one primary, one secondary
and one tertiary, it would be easy to distinguish the tertiary
alcohol.

After warming, the orange dichromate(VI) ions have been

reduced to green chromium(III) ions by the primary and
secondary alcohols. This shows that both the primary and
secondary alcohols have been oxidised but the tertiary alcohol,
2-methylpropan-2-ol, has not.
CARBOXYLIC ACID
❑ Further oxidation of the aldehyde yields the carboxylic acid.
❑ Carboxylic acids are also made from nitriles under reflux,
CARBOXYLIC ACID
Some common reactions of carboxylic acid
1. as an acid
✓ CH3COOH + NaOH → CH3COONa + H2O
✓ 2CH3COOH + Mg → (CH3COO)2Mg + H2
✓ 2CH3COOH + K2CO3 → 2CH3COOK + H2O + CO2

2. Making acyl chlorides

✓ CH3COOH + PCl5 → CH3COCl + POCl3 + HCl
No special conditions are required for this reaction

✓ 3CH3COOH + PCl3 → 3CH3COCl + H3PO3

Heat is required for this reaction.

✓ CH3COOH + SOCl2 → CH3COCl + SO2 + HCl

No special conditions are required for this reaction.
3. Reduction of carboxylic acid
✓ Carboxylic acids can be reduced to their corresponding primary
alcohol by using the reducing agent lithium
tetrahydridoaluminate LiAlH4, in dry ether at room temperature.
Dry ether is used because LiAlH4 reacts violently with water.
 ECQ
1 Carboxylic acids are reduced to alcohols by lithium
tetrahydridoaluminate, LiAlH4 , in dry ether. Complete the
following equations. Use [H] to represent the hydrogen
from the reducing agent.

CH3COOH + __________ → CH3CH2OH + H2O

CH3CH2COOH + _______ → ___________ +__________

HOOCCH2CH2COOH + ________ → _________ + __________

2 Give the structure and name the ester formed when:
a. ethanol reacts with butanoic acid
b. propanol reacts with hexanoic acid
c. methanol reacts with pentanoic acid.

3 Esters can also be hydrolysed by refluxing with

concentrated aqueous sodium hydroxide. Write equations
for the alkaline hydrolysis of these esters:
a. propyl methanoate
b. methyl ethanoate
c. butyl propanoate