Unit 2 Module 1 Carboxylic acids and their derivatives page 1 of 8

CARBOXYLIC ACIDS AND DERIVATIVES

Structure of a typical carboxylic acid

This group is the functional group

This is an example of an aliphatic acid

Aromatic carboxylic acids have a carboxyl group attached directly to an

aromatic ring.

Reactions of carboxylic acids

1. With highly reactive metals and inorganic bases/alkalis to form the

salt and hydrogen gas for highly reactive metals and a salt and
water formed from inorganic bases

2CH3COOH(aq) + Na(s)  CH3COONa(aq) + H2(g)

ethanoic sodium sodium hydrogen
acid ethanoate gas

2CH3COOH(aq) + NaOH(aq)  CH3COONa(aq) + H2O(l)

ethanoic sodium sodium water
acid hydroxide ethanoate

2. Amide formation
Amides have the
With ammonia to form an ammonium
functional group below
salt, which then decomposes by heat
(remember this reaction is
done in reflux) to form an amide

RCOOH + NH3  RCOO-NH4+

RCOO-NH4+  RCONH2 + H2O
Unit 2 Module 1 Carboxylic acids and their derivatives page 2 of 8

3. Ester formation

Reflux with alcohols in the presence of conc. sulphuric acid and 170 °C
to form an ester and water (Note esters are low molecular mass
compounds, which have sweet smells and are insoluble in water)

RCOOH + R1OH conc.H2SO4 RCOOR1 + H2O

4. Acid chloride formation

Acid chlorides
With chlorinating agents e.g. dichlorosulphur have the following
(IV) oxide SOCl2 or phosphorous (V) chloride functional group
PCl5 to form an acid chloride
RCOOH PCl5 or SOCl2 RCOCl + HCl

5. With carbonates and hydrogen carbonates

to give a salt, carbon dioxide and water

2RCOOH + Na2CO3  2RCOO-Na+ + CO2 + H2O

RCOOH + NaHCO3  RCOO-Na+ + CO2 + H2O

6. Reduction

With LiAlH4 or any other reducing agent to form the corresponding alcohol
RCOOH LiAlH4 (in ether) RCH2OH

7. Anhydride formation

When 2 molecules of a carboxylic acid is reacted with a dehydrating

agent such as phosphorous (V) oxide P 4O10, a molecule of water is
eliminated and an acid anhydride is formed.

2RCOOH distilled in P4O10 (RCO)2O

Unit 2 Module 1 Carboxylic acids and their derivatives page 3 of 8
Checkpoint A
Unit 2 Module 1 Carboxylic acids and their derivatives page 4 of 8
Reactions of acid derivatives

1. Hydrolysis
Acid chlorides are hydrolysed to give carboxylic acid and hydrogen
chloride gas RCOCl + H2O  RCOOH + HCl

Esters are also hydrolysed to give the original alcohol and if the reagent
is a strong mineral acid, then the carboxylic acid is formed
RCOOR1 + H+  ROH + RCOOH
If the reagent is a strong alkali, then the original alcohol is formed and
the salt of the carboxylic acid RCOOR 1 + OH-  ROH + RCOO-

2. Ester formation
Acid and aroyl chlorides react readily with
a) alcohols to form an ester and hydrogen chloride gas
b) phenols in alkaline solutions to form an ester and hydrogen chloride
gas

3. Amide formation
Amides are formed by reaction of acid chlorides with ammonia and with
primary and secondary amines

RCOCl + NH3  RCONH2 + HCl

RCOCl + R2NH  RCONR2 + HCl

4. Anhydride formation
When an acid chloride is heated with the sodium salt of a carboxylic acid, the
acid anhydride is formed
RCOCl + RCOO-Na+  (RCO)2O + NaCl

NB acid anhydrides react in a similar way to acid chlorides; they form esters
with alcohols and phenols and they form amides with ammonia and primary
and secondary amines.
Unit 2 Module 1 Carboxylic acids and their derivatives page 5 of 8
Checkpoint B

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Saponification (alkaline hydrolysis of fats/oils)

When fats/oils are hydrolysed by an alkali, “soap” is produced.

How is a fat/oil molecule formed?

By the reaction of glycerol and long chain fatty acids (carboxylic acids with
hydrocarbon chains containing 12 or more carbon atoms)

Glycerol is propane-1,2,3-triol

Long chain fatty acids could be: C15H31COOH palmitic acid (saturated),
C17H35COOH stearic acid (saturated)
C17H33COOH oleic acid (unsaturated)
Unit 2 Module 1 Carboxylic acids and their derivatives page 6 of 8

When a fat/oil molecule is hydrolysis by an alkali, the glycerol is formed as

well as the sodium salt of the long chain fatty acid. The sodium salt of the
acid is the soap.

Transesterification biodiesel production

Biodiesel production is the act of producing the biofuel, biodiesel, through
either transesterification or alcoholysis. The process involves reacting
vegetable oils or animal fats catalytically with a short-chain aliphatic
alcohols (typically methanol or ethanol).

The vegetable oil is reacted with alkali in the presence of ethanol or

methanol as a catalyst under reflux, which produces the esters of the fatty
acids and glycerol. The biodiesel is the collection of the esters produced.

Checkpoint C

What advantages would there be for the use of biodiesel or biofuel in

general?
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Unit 2 Module 1 Carboxylic acids and their derivatives page 7 of 8
Explanation of relative acidities of acids and chlorine substituted acids

Carboxylic acids are only partially ionised in aqueous solution, making them
weak acids.

The relative strength of acids is attributed to the stability of the acid anion.
The more stable the acid anion, the stronger the acid.

The longer the hydrocarbon acid, the WEAKER the acid. However, the
more electronegative atoms present in the molecule e.g. Cl atoms present in
the aliphatic chain the STRONGER the acid.

In order of DECREASING ACID STRENGTH of aliphatic acids

(Cl)3CCOOH CH(Cl)2COOH CH2ClCOOH

CH3COOH CH3CH2COOH

In aliphatic acids, the more electron withdrawing groups present, this represents a
GREATER spreading of the charge on the oxygen atom (from the anion formed
from dissociation in aqueous solution) which results in a more stable acid anion.
Therefore trichloroethanoic acid is more acidic than dichloroethanoic acid etc.

Propanoic acid is a weaker acid than ethanoic acid since the hydrocarbon chain is
longer. NB The lower the pKa value, the stronger the acid.
Note that aliphatic alcohols show the weakest acidic character, then phenols
are stronger and finally carboxylic acids show the strongest acidic character.

The acid anion of carboxylic acids are therefore the most stable, then the
acid anion from phenols and finally the acid anion from ethanol.
Note that acid chlorides are MORE reactive than corresponding carboxylic
acids.
Unit 2 Module 1 Carboxylic acids and their derivatives page 8 of 8
Checkpoint C