29 December 2010

16:26

Carboxylic Acids

The organic compounds containing a carboxyl group are called carboxylic acids.

For example, acetic acid, CH3 COOH.

The general formula of monocarboxylic acids is CnH2 nO2 / CnH2 n+1 COOH.
They are represented as where R is an alkyl group (except formic acid where

R is a hydrogen atom).

Nomenclature of Acids
(i) Common Name: The lower members are known by the names derived from the source
(origin).
For example, HCOOH formic acid (obtained from red ant known as 'formica' in Latin)
CH3  COOH, acetic acid (obtained from vinegar known as 'acetum' in Latin)

(ii) IUPAC Name: The suffix e of the corresponding alkane is replaced by oic acid.
For example, H  COOH, Methanoic acid; CH3  COOH, Ethanoic acid.

Structure of Carbon Atom

In the carboxylic acid group (COOH), the carbon atom is sp2 hybridised.

Formic Acid (HCOOH)

Formic acid contains both aldehyde group and acid group. Hence, it shows
the
reducing properties of aldehydes, i.e. it can reduce Fehling's solution, Tollen's reagent, etc.

Preparation of Monocarboxylic Acids

a. By Oxidation:
i. From Primary Alcohols:
RCH2 OH + [O] RCHO + H2 O

RCHO + [O] RCOOH

iii. From Aldehydes:
RCHO + [O] RCOOH

b. By Hydrolysis of Alkyl Cyanides (Nitriles):

i. Using Acids:
RC  N + 2H2 O RCOOH + NH3

ii. (NH3 + HCl  NH4 Cl)

iii. Using Alkalies:
R C  N + H2 O RCOONa + NH3

iv. R COONa + HCl  RCOOH + NaCl

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 iv. R COONa + HCl  RCOOH + NaCl
c. By Grignard Reagent and Solid Carbon Dioxide:
It is a nucleophilic addition reaction.
+ RMgX

Properties
Carboxylic acids are weak acids. The acidic nature of carboxylic acid decreases as the
molecular weight increases. This acidic nature is due to the resonance stabilisation of
carboxylate ion.
R • OH + H2 O
H3 O+ +
Among all the acids, formic acid is the strongest acid.

Reactions:
a. Acidic Properties:
They undergo nucleophilic substitution reactions.
i. Reaction with Reactive Metals (M) like Na, K:
2R  COOH + 2M  2R  COOM + H2
ii. Reaction with Alkalies:
R  COOH + NaOH R COONa + H2 O
(or KOH) (or R COOK)
iii.
iv. Reaction with Carbonates and Bicarbonates:
2RCOOH + Na2 CO3  2 R  COONa + H2 O + CO2
RCOOH + NaHCO3  RCOONa + H2 O + CO2
v. Reaction with Ammonia:
RCOOH + NH3 RCOONH4
b. Anhydride Formation:

P2 O5 + H2 O
2HPO3
metaphosphoric acid
c. Esterification:
RCOOH + R  OH R COO • R` +H2 O
ester

The reverse of esterification is known as hydrolysis.

D. Amide Formation:
RCOOH + NH3

RCOONH4

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RCOONH4
RCOONH4 R CONH2 +H2 O
amide

Esters:
The derivatives of carboxylic acids, in which the 'H' atom of the carboxylic group is replaced
by an alkyl group, are called esters.
They are the condensation products of acids and hydroxy compounds. They have general
formula, R COOR where R is an alkyl group. For example: Ethyl acetate, CH3 COOC2 H5 .

Nomenclature of Esters
i. Common Name: Esters are named by replacing the suffix ic acid of the
carboxylic acid by ate and adding the name of alkyl group of the alcohol as a
separate word before it.
ii. IUPAC System: Esters are named as alkyl alkanoate. For example: HCOOCH3 ,
methyl methanoate.

Preparation of Esters
a. From Carboxylic Acids and Alcohols (Esterification):
RCOOH + R OH R COOR+H2 O
b . From Acid Anhydrides and Alcohols:

c. From Acid Chlorides and Alcohols:

R CO Cl + H O  R' R COOR' + HCl

d. From Silver Salt of an Acid and Alkyl Halide:

R COO Ag + X  R' R COOR' + AgX

Reactions of Ethyl Acetate

a. Hydrolysis:
i. Acid Hydrolysis:
CH3 COOC2 H5 + H  OH CH3 COOH + C2 H5 OH

acid (H+)
ii.
iii. Alkaline Hydrolysis:
CH3 COOC2 H5 + NaOH CH3 COONa + C2 H5 OH

iv.
a. Action of Grignard Reagent:

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 With excess of Grignard reagent:

Important Uses of Esters:

i. Esters are used as solvents for inks, paints, oils, gums, resins, etc.
ii. As esters have a pleasant smell, they are used in the manufacture of perfumes,
essences, and flavouring agents. For example, isoamyl acetate is used as banana
flavour, methyl butyrate as pineapple flavour, octyleacetate as orange flavour.
iii. Esters are used as plasticizers in the manufacture of plastics.
iv. Esters are used as perfumes in soaps, cosmetics, etc.

Pasted from <http://www.indicareer.com/entrance-exams/mht-cet/chemistry/Acids-and-Esters-1.html>

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