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Carboxylic acids and their derivatives

Learning Objectives
Students should be able to

Interpret and use the nomenclature, general
formula and displayed formula of the carboxylic
acids and esters
Describe the formation of carboxylic acids from
alcohols, aldehydes and nitriles
Describe the reactions of carboxylic acids in the
formation of
(i) salts
(ii) Esters
continued on next page....

Carboxylic acids and their derivatives
Learning Objectives continued...

Describe the formation of esters from carboxylic
acids , using ethyl ethanoate as an example

Describe acid and base hydrolysis of esters

State the major commercial uses of esters e.g.
Solvents , perfumes and flavourings

STRUCTURE OF CARBOXYLIC ACIDS
contain the carboxyl functional group -COOH

the bonds around carbon atom are in a planar arrangement



include a carbonyl (C=O) group and


a hydroxyl (O-H) group


are isomeric with esters :- RCOOR
Carboxylic acids form a homologous series
HOMOLOGOUS SERIES
HCOOH CH
3
COOH C
2
H
5
COOH
With more carbon atoms, there can be structural isomers
C
3
H
7
COOH (CH
3
)
2
CHCOOH
Greater branching causes inter-molecular forces to be
weaker giving rise to lower boiling points
Boiling point is higher for straight chain isomers.
101C 118C 141C 164C
164C 154C
PHYSICAL PROPERTIES
BOILING POINT

Increases as molecular size increases - due to increased strength of van
der Waals forces
PHYSICAL PROPERTIES
BOILING POINT

Carboxylic acids have high boiling points for their relative molecular mass

This is caused by inter-molecular hydrogen bonding due to polar OH
bonds








DIMERISATION

stronger inter-molecular attraction means more energy is needed to
separate molecules
HYDROGEN
BONDING
PHYSICAL PROPERTIES
SOLUBILITY

carboxylic acids are soluble in organic solvents

they are also soluble in water due to hydrogen bonding








small molecules dissolve readily in cold water

as mass increases, the solubility decreases

benzoic acid is fairly insoluble in cold water but is soluble in hot water
HYDROGEN
BONDING
PREPARATION OF CARBOXYLIC ACIDS

Oxidation of aldehydes RCHO + [O] > RCOOH

Hydrolysis of esters RCOOR + H
2
O RCOOH + ROH

Hydrolysis of acyl chlorides RCOCl + H
2
O > RCOOH + HCl

Hydrolysis of nitriles RCN + 2 H
2
O > RCOOH + NH
3


Hydrolysis of amides RCONH
2
+ H
2
O > RCOOH + NH
3


Oxidation of 1alcohols RCH
2
OH + 2[O] > RCOOH + H
2
O


CHEMICAL PROPERTIES
ACIDITY

weak acids RCOOH + H
2
O(l) RCOO(aq) + H
3
O
+
(aq)


form salts RCOOH + NaOH(aq) > RCOONa
+
(aq) + H
2
O(l)

2RCOOH + Mg(s) > (RCOO)
2
Mg
2+
(aq) + H
2
(g)


The acid can be liberated from its salt by treatment with a stronger acid.

e.g. RCOO Na
+
(aq) + HCl(aq) > RCOOH + NaCl(aq)

Conversion of an acid to its water soluble salt followed by acidification of
the salt to restore the acid is often used to separate acids from a mixture.



Carboxylic acids are strong enough acids to liberate CO
2
from carbonates

ESTERIFICATION
Reagent(s) alcohol + strong acid catalyst (e.g conc. H
2
SO
4
)
Conditions reflux
Product ester
Equation e.g. CH
3
CH
2
OH(l) + CH
3
COOH(l) CH
3
COOC
2
H
5
(l) + H
2
O(l)
ethanol ethanoic acid ethyl ethanoate

Notes Conc. H
2
SO
4
is a dehydrating agent - it removes water
causing the equilibrium to move to the right and thus
increases the yield of the ester


Naming esters Named from the original alcohol and carboxylic acid

CH
3
OH + CH
3
COOH CH
3
COOCH
3
+ H
2
O
METHYL ETHANOATE
ESTERS
Structure Substitute the H in carboxylic acid by an organic group

Nomenclature first part from alcohol, second part from acid
e.g. methyl ethanoate CH
3
COOCH
3









Preparation From carboxylic acids and acyl chlorides

Reactivity Unreactive compared with acids and acyl chlorides

Isomerism Esters are structural isomers of carboxylic acids
ETHYL METHANOATE
METHYL ETHANOATE
Classification CARBOXYLIC ACID ESTER

Functional Group R-COOH R-COOR

Name PROPANOIC ACID METHYL ETHANOATE

Physical properties O-H bond gives rise No hydrogen bonding
to hydrogen bonding; insoluble in water
get higher boiling point
and solubility in water

Chemical properties acidic fairly unreactive
react with alcohols hydrolysed to acids
STRUCTURAL ISOMERISM FUNCTIONAL GROUP
PREPARATION OF ESTERS - 1
Reagent(s) alcohol + carboxylic acid

Conditions reflux with a strong acid catalyst (e.g. conc. H
2
SO
4
)


Equation e.g. CH
3
CH
2
OH(l) + CH
3
COOH(l) CH
3
COOC
2
H
5
(l) + H
2
O(l)
ethanol ethanoic acid ethyl ethanoate



Note Conc. H
2
SO
4
is a dehydrating agent - it removes water
causing the equilibrium to move to the right and thus
increases the yield of the ester



PREPARATION OF ESTERS - 2
Reagent(s) alcohol + acyl chloride

Conditions reflux under dry conditons


Equation e.g. CH
3
OH(l) + CH
3
COCl(l) > CH
3
COOCH
3
(l) + HCl(g)
methanol ethanoyl methyl
chloride ethanoate


Note Acyl chlorides are very reactive
but must be kept dry as they react
with water.
CHLORINATION OF CARBOXYLIC ACIDS ( Acylation)
Chlorination involves replacing the OH with a Cl

Product acyl chloride

Reagent thionyl chloride SOCl
2

Conditions DRY conditions

Equation CH
3
COOH + SOCl
2
> CH
3
COCl + SO
2
+ HCl




Alternative
method CH
3
COOH + PCl
5
> CH
3
COCl + POCl
3
+ HCl
phosphorus(V) chloride

HYDROLYSIS OF ESTERS
Hydrolysis is the opposite of esterification

ESTER + WATER CARBOXYLIC ACID + ALCOHOL

HCOOH + C
2
H
5
OH
METHANOIC ETHANOL
ACID
CH
3
COOH + CH
3
OH
ETHANOIC METHANOL
ACID
ETHYL METHANOATE
METHYL ETHANOATE
HYDROLYSIS OF ESTERS

The products of hydrolysis depend on the conditions used...




acidic CH
3
COOCH
3
+ H
2
O CH
3
COOH + CH
3
OH

alkaline CH
3
COOCH
3
+ NaOH > CH
3
COO Na
+
+ CH
3
OH

If the hydrolysis takes place under alkaline conditions,
the organic product is a water soluble ionic salt

The carboxylic acid can be made by treating the salt with HCl

CH
3
COO Na
+
+ HCl > CH
3
COOH + NaCl

USES OF ESTERS
Despite being fairly chemically unreactive, esters are useful as ...

flavourings apple 2-methylbutanoate

pear 3-methylbutylethanoate
banana 1-methylbutylethanoate
pineapple butylbutanoate
rum 2-methylpropylpropanoate


solvents nail varnish remover - ethyl ethanoate