Carboxylic acid

Chapter 10

Nomenclature of
Carboxylic Acids
The longest chain must contain the
carboxyl group.
The carboxyl group is at the terminal,
therefore the carbon of the carboxyl group
is not numbered.
One COOH carboxyl group is at one end
Two COOH carboxyl groups are at both
ends
Name the compound as alkane, drop e
in alkane and add oic acid (eg:

CH3

Br

CH3

CH

CH

O
CH2 C

OH

4-bromo-3-methylpentanoic acid
If, two COOH groups, the compound will be
named as alkanedioic acid

HO

CH2 CH2 CH2 C

OH

pentanedioic acid

Name the followings :

CH3

1.

HO

CH CH2 CH2 CH2 C OH

O

2.

HO
3.

CH3

C CH2 CH

COOH

CH

CH

CH3

COOH
COOH

4.

CH3
5.

Br

CH3
COOH

COOH

6.

Cl

7.

COOH

Odour
lower aliphatic carboxylic acid-pungent
eg : ethanoic acid (vinegar)
unpleasant odours as chain gets larger
eg : butanoic (perspiration)
pentanoic acid (rancid acid)
hexanoic acid (vomit)
Taste
Sour

Boiling Point
The boiling point of carboxylic acid is higher than an alcohol,
a ketone or an aldehyde (with Mr that almost the same)
because:
i.

it exists as stable dimers that form hydrogen

bond.

ii.

molecules in dimers are arranged closely packed,

therefore the hydrogen bonds are relatively strong.

iii.

high energy is needed to overcome the

intermolecular forces ,
boiling point

Hydrogen bond
O
R

O
C

C
O

O
Hydrogen bond

Solubility
Solubility in water
Carboxylic acids are soluble in water due to
the formation of hydrogen bond between the
water molecules and carboxylic acid
molecules.
Hydrogen Bonds

O
R

H
O

C
O

C
H

Aromatic carboxylic acids are slightly

soluble in water due to the huge
aromatic ring.
Dicarboxylic acids are relatively more
soluble since more hydrogen bonds
are formed.

Preparation of Carboxylic acid

Oxidation

Carbonation of Grignard Reagent

Hydrolysis of Nitrile Compound

Reactions of Carboxylic Acid

1. Reaction with NaOH (NEUTRALISATION)

O
R

O
+ NaOH

+ H2 O
-

O Na+

OH
COO

COOH

+ NaOH

+ H2 O

2. Reaction with Electropositive Metal

O

O
R

C OH

C O M

3. Reaction with NaHCO3 (sodium bicarbonate)

H2

Acyl chloride can be prepared from the reaction of

carboxylic acids with thionyl chloride, SOCl2 ;
phosphorous pentachloride, PCl5 ; phosphorous
trichloride, PCl3
O
SOCl2

O
R

C OH

C Cl + SO2 + HCl
O

PCl5

C Cl + POCl3 + HCl

5. Esterification

Carboxylic acids react with alcohols

in the presence of mineral acid
catalyst to produce esters.
O
R

O
OH + HOR

carboxylic acid

alcohol

H+

C
ester

O R' + H2O

6. Acid Anhydride Formation

Acid anhydrides can be prepared from

carboxylic acids by the loss of water through
heating.
O
O
O
O
R

C OH + HO C

heat

R C

C R + H2 O

acid anhydride

7. Acid Anhydride Formation

Reaction of carboxylic acids with an ammonia or

O
amine give amide.
NH3
R C NH2 + H2O
1o amide

O
O
R

C OH

RNH2
(1o amine)

NHR + H2O

2o amide

O
R2NH
(2 amine)
o

NR2 + H2O

(3o amide)

8. Reduction

Carboxylic acid are reduced to primary

alcohols by reaction with lithium
aluminium hydride, LiAlH4 or Ni.
O
R

R'

Ni / H2
180C

R CH2 OH
1o alcohol

Este
rs

Nomenclature of
Ester
Esters are named
by first naming the group that came
from the alcohol.
This word is followed by a space and then the name
of the acid is changed by
dropping the -oic acid ending of the parent acid and
adding -oate.

Ethyl ethanoate
Esters have same molecular formula as carboxylic
acids but are neutral compounds

Draw the structure of these esters :

1. methyl ethanoate
2. ethyl ethanoate
3.

phenyl ethanoate

4. methyl benzoate

Physical
Properties

The boiling points of esters are lower than carboxylic acid

Compounds

Example

Boiling point

Ester

Methyl
methanoate

31.5 C

Carboxylic acid

Ethanoic acid

117.9 C

Carboxylic acids has higher boiling point than ester.

Carboxylic acids able to form strong hydrogen bond
between molecules.
Esters have weaker van der Waals forces between
molecules.

Hydrolysis of Esters
Ester hydrolysis
Alkaline
hydrolysis

Sodium salt + alcohol

Acid
Hydrolysis

Acid + alcohol

Acid Hydrolysis of Esters

Alkaline Hydrolysis of Esters

Hydrogenatio
n of oils

Oils and fats are naturally occurring esters of long

chain fatty acids and glycerol.

The carboxylic acid components are called fatty acids.

Fatty acids are divided into saturated (stearic acid) and unsaturated
(oleic acid).

Oils can be converted to fats by hydrogenation reaction.

Margarines are made by hydrogenation of vegetable oils.

Soaps and detergents

Soaps
Soaps are saponification / alkaline hydrolysis of ester
(Soap can be obtained through the reaction of alkaline hydrolysis of ester)

Example of soaps
sodium stearate
sodium palmitate

NaC17H35COO
NaC17H31COO
O
C

nonpolar
O

polar

Soap is an emulsifying agent because the ionic end is

water soluble and the hydrocarbon end is fat soluble.

Cleaning action of soap

1. Long non-polar hydrocarbon chain dissolves in

2. Agitation will cause the grease drops to be lift

3. Emulsified grease drops exist as micelles
which repel due
to the charged heads of the soap ions

4. Micelles suspended in solution is therefore wa

Detergents

most laundry detergents contain tripolyphosph

3 phosphoric acids join to make tripolyphospho

H5P3O10 + 5 NaOH

Na5P3O10 + 5 H2O

Problem with phosphates in waste water will

over-fertilize
natural
waters.
This causes
massive growth of blue-green
algae which
depletes the water of more oxygen