Methanoic acid and ethanedioic acid

Generally, carboxylic acid does not undergo oxidation and dehydration easily.
Methanoic acid and ethanedioic acid are exceptions.
Methanoic acid, HCOOH

O
H C OH

The presence of aldehyde group

enables HCOOH to be oxidised
by mild oxidising agents.

HCOOH and (COOH)2 are

reducing agents.

Ethanedioic acid, (COOH)2

O O
HO C

ALL other carboxylic

acids do not show
reducing property.

C OH

Methanoic acid:
Oxidation:

KMnO4/H+

HCOOH + [O]

CO2 + H2O

HCOOH + 2[Ag(NH3)2]+ + 2OHHCOOH + 2Cu2+ + 6OHO

Dehydration:

(NH4)2CO3 + 2Ag + 2NH3 + H2O

CO32- + Cu2O + 4H2O

conc. H2SO4

C OH

CO + H2O

Ethanedioic acid:

(COOH)2 + [O]

Oxidation:

KMnO4/H+

2CO2 + H2O

Ethanedioic acid cannot be oxidised by Tollens reagent and Fehlings solution.

It does not contain alddehyde group.
O O

Dehydration:

HO C

C OH

conc. H2SO4

CO2 + CO + H2O

Comparing methanoic acid, ethanoic acid (typical carboxylic acid) and ethanedioic acid:
Chemical
Test
PCl5, r.t.p.

KMnO4/ H+,
Reflux

Methanoic acid, HCOOH

Ethanoic acid,
CH3COOH

Ethanedioic acid,
(COOH)2

White fume (HCl).

HCOOH + PCl5 CO +
2HCl + POCl3

White fume (HCl).

CH3COOH + PCl5
CH3COCl + HCl + POCl3

White fume (HCl).

(COOH)2 + 2PCl5
(COCl)2 + 2HCl + 2POCl3

Purple to colourless.
HCOOH + [O]
KMnO4/H+

Tollens

KMnO4/H+

CO2 + H2O

Silver mirror is formed.

Purple to colourless.
(COOH)2 + [O]

2CO2 + H2O
-

reagent
(only with
CHO)
Conc.
H2SO4,
heat

CO(g) is liberated.

CO(g) and CO2(g) are

liberated. Limewater turns
chalky.

Methanoic acid, HCOOH

Ethanoic acid,
CH3COOH

Ethanedioic acid,
(COOH)2

PCl5, r.t.p.
PCl3
SOCl2

KMnO4/ H+,
reflux

Tollens
reagent

Conc.
H2SO4,
heat

/
A gas that turns limewater
chalky is formed/

Chemical
Test

Uses:
To coagulate latex: Methanoic acid and ethanoic acid
In food industry:
o Vinegars: Ethanoic acid
o Food preservatives: Benzoic acid
Perfumery: Derivatives of carboxylic acid, ester.
Medical purpose:
o Antiseptic: Salicylic acid/ 2-hydroxybenzoic acid
o Aspirin/ Methyl salicylate: Manufactured from salicylic acid/ 2-hydroxybenzoic acid