Professional Documents
Culture Documents
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