6.1.

3 Carboxylic Acids and Esters

Solubility in Water 
O
Acidity The smaller carboxylic (up to C4) 
H3C C 
The carboxylic acid are only weak acids acids dissolve in water in all 
  H
in water and only slightly dissociate, but proportions but after this the solubility
they are strong enough to displace rapidly reduces. They dissolve O
 H :O
carbon dioxide from carbonates. because they can hydrogen bond to H
the water molecules.
CH3CO2H(aq) CH3CO2-(aq)+ H+(aq)

Delocalisation
The delocalised ion has equal C-O bond lengths. If
The carboxylic acid salts are stabilised by delocalisation, delocalisation did not occur, the C=O bond would be
which makes the dissociation more likely. shorter than the C-O bond.

O O The pi charge cloud has O

delocalised H3C C delocalised and spread out. The
H3C C delocalisation makes the ion C
H3C
OH O more stable and therefore more
likely to form.
O
Strength of carboxylic acids

O O Increasing chain length pushes

delocalised electron density on to the COO-
H3C CH2 C H3C CH2 C
ion, making it more negative and
OH O less stable. This make the acid
less strong.
Alkyl groups electron releasing
Propanoic acid less acidic than ethanoic acid
Cl O Cl O Electronegative chlorine atoms
H C C delocalised withdraw electron density from
H C C the COO- ion, making it less
OH negative and more stable. This
H O
H make the acid more strong.
Chlorine electron withdrawing
chloroethanoic acid more acidic than ethanoic acid

Salt formation reactions of carboxylic acids

Carboxylic acids can form salts with metals, alkalis and
carbonates.
acid + metal (Na)  salt + hydrogen The effervescence caused by production of CO2
CH3CO2H + Na  CH3CO2-Na+ + H2 with carboxylic acids with solid Na2CO3 or
aqueous NaHCO3 can be used as a functional
acid + alkali (NaOH)  salt + water group test for carboxylic acids
CH3CO2H + NaOH  CH3CO2-Na+ + H2O

acid + carbonate (Na2CO3)  salt + water + CO2

2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2

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 Oxidation of methanoic acid O O It forms carbonic acid
Carboxylic acids cannot be oxidised by using (H2 CO3 ) which can
oxidising agents but methanoic acid is an H C + [O]  H O C decompose to give
exception as its structure has effectively an
O H O H CO2
aldehyde group

Esterification
H H O H Esters have two parts
Carboxylic acids react with alcohols, in the to their names, eg
presence of a strong sulfuric acid catalyst, H C C C O C H methyl propanoate.
to form esters and water. H H H
H+ The bit ending in –anoate The bit ending in –yl comes from
Carboxylic Acid + Alcohol Ester + water comes from the carboxylic the alcohol that has formed it
acid and includes the C in and is next to the single bonded
the C=O bond. oxygen.

H H H O H H
O The reaction is reversible. The
H+ reaction is quite slow and needs
+ H C C O H H C C O C C H + H2O
H3C C heating under reflux, (often for
OH H H H H H several hours or days). Low yields
(50% ish) are achieved. An acid
CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O catalyst (H2SO4) is needed.
Ethanoic acid Ethanol Ethyl Ethanoate

Esterification using acid anhydrides

The acid anhydrides are more
Change in functional group: acid anhydride  ester reactive than carboxylic acids.
Reagent: alcohol The reaction is not reversible
and a higher yield is achieved.
Conditions: room temp.

(RCO)2O + CH3CH2OH  RCO2CH2CH3 +RCO2H

O
H O H H
CH3 C
+ CH3CH2OH  H C C O C C H + CH3CO2H
O
CH3 C H H H
O

Hydrolysis of esters Esters can be hydrolysed and split up by either heating with acid or with sodium hydroxide.

i) with acid
This reaction is the reverse reaction of ester formation. When an
reagents: dilute acid (HCl)
ester is hydrolysed a carboxylic acid and an alcohol are formed.
conditions: heat under reflux
H+
This reaction is reversible and does
CH3CH2CO2CH2CH3 + H2O CH3CH2CO2H + CH3CH2OH
not give a good yield of the products.
ethyl propanoate

ii) with sodium hydroxide

reagents: dilute sodium hydroxide CH3CH2CO2CH3 + NaOH  CH3CH2CO2- Na+ + CH3OH
conditions: heat under reflux methyl propanoate sodium propanoate methanol

The carboxylic acid salt product is the anion of the carboxylic acid.
This reaction goes to completion. The anion is resistant to attack by weak nucleophiles such as alcohols,
so the reaction is not reversible.
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Acyl Chlorides
O The Cl group is classed as a good leaving groups (to
Acyl chlorides are
do with less effective delocalisation.) This makes acyl
CH3 C much more reactive
chlorides much more reactive than carboxylic acids
than carboxylic acids and esters.
Cl
ethanoyl chloride

Formation of acyl chloride from a carboxylic acid

Reaction: carboxylic acid  acyl chloride

Sulfur dichloride oxide (thionyl
Reagent: SOCl2
chloride) SOCl2 is a liquid
Conditions: room temp

CH3COOH + SOCl2  CH3COCl + SO2 + HCl

O O
+ SOCl2  + SO2 + HCl
H3C C H3C C
OH Cl

Reactions of acyl chlorides

Reaction with water Reaction with alcohol

Change in functional group: acyl chloride  Change in functional group: acyl chloride  ester
carboxylic acid Reagent: alcohol
Reagent: water Conditions: room temp.
Conditions: room temp.
RCOCl (l) + CH3CH2OH  RCO2CH2CH3 + HCl (g)
RCOCl (l) + H2O  RCO2H + HCl (g)
O H O H H
O O CH 3 C + CH3CH2OH  H C C O C C H + HCl
CH3 C + H2O  CH3 C + HCl (g) Cl H H H
Cl OH
Observation: Steamy white fumes of HCl are
Observation: Steamy white fumes of HCl
given off
are given off

This reaction for making esters is much better than using

carboxylic acids as the reaction is much quicker and it is
not a reversible reaction

Reaction with ammonia Reaction with primary amines

Change in functional group: acyl chloride  Change in functional group: acyl chloride 
primary amide secondary amide
Reagent: ammonia Reagent: primary amine
Conditions: room temp. Conditions: room temp.

RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl-

RCOCl (l) +2NH3  RCONH2 + NH4Cl (s)
O O O
O + CH3NH3+Cl-
+ 2CH3NH2  CH3 C NH CH3
CH3 C + 2NH3  CH3 C + NH4Cl (s) CH3 C

Cl NH2 Cl
N-methylethanamide
Observation: white smoke of NH4Cl is given off

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Reaction with phenol

Change in functional group: acyl chloride  ester

Reagent: phenol
Conditions: room temp.

RCOCl (l) + C6H5OH  RCO2C6H5 + HCl (g)

O
O O + HCl
CH 3 C + OH C
Cl
H3C
Observation: Steamy white fumes of HCl
are given off

Phenols do not easily form esters with carboxylic

acids but do so readily with acyl chlorides

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