Chemistry of Nitrous Acid


1. Introduction to Nitrous Acid

Nitrous Acid (HNO₂) is a weak, unstable acid known only in solution or in the form of nitrite salts. It is a key reagent in the dye industry.

Appearance: Pale blue solution (due to dissolved N₂O₃)
Molecular Formula: HNO₂
Molar Mass: 47.01 g/mol
Oxidation State of Nitrogen: +3


2. Preparation

Because it is unstable, it is prepared in situ (on the spot) by reacting a nitrite salt with a cold mineral acid:

NaNO₂ + HCl → NaCl + HNO₂

3. Chemical Properties

a) Instability (Disproportionation)

At room temperature, nitrous acid decomposes into nitric acid and nitric oxide:

3HNO₂ → HNO₃ + 2NO + H₂O

b) Dual Role: Oxidizing & Reducing Agent

Since Nitrogen is in the +3 oxidation state (intermediate), it can be oxidized to +5 or reduced to lower states.

  • As an Oxidant: 2HI + 2HNO₂ → I₂ + 2NO + 2H₂O
  • As a Reductant: HNO₂ + H₂O₂ → HNO₃ + H₂O

c) Reaction with Organic Compounds (Diazotization)

This is the most industrially significant reaction. At low temperatures (0–5°C), it reacts with aromatic primary amines to form diazonium salts:

C₆H₅NH₂ + NaNO₂ + 2HCl → C₆H₅N₂⁺Cl⁻ + NaCl + 2H₂O


4. Structure

Nitrous acid exists in two isomeric forms: cis and trans. The trans form is generally more stable at room temperature.

5. Uses

  • Preparation of diazonium salts for azo dyes.
  • Removal of toxic sodium azide.
  • In physiological studies as a vasodilator (via conversion to NO).

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