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Nitrous Acid (HNO2) Reagent | chemca

Nitrous Acid (HNO2) Reagent | chemca
Reagents

Nitrous Acid ($HNO_2$)

Reaction with $1^\circ, 2^\circ, 3^\circ$ Amines (Aliphatic vs Aromatic).

By chemca Team • Updated Jan 2026

Nitrous Acid ($HNO_2$) is an unstable weak acid. It is prepared in situ by reacting Sodium Nitrite ($NaNO_2$) with dilute Hydrochloric Acid ($HCl$) at low temperatures ($0-5^\circ C$). It is primarily used to distinguish between primary, secondary, and tertiary amines.

$$ NaNO_2 + HCl \xrightarrow{0-5^\circ C} HNO_2 + NaCl $$

1. Reaction with Primary ($1^\circ$) Amines

A. Aliphatic Primary Amines

React with $HNO_2$ to form unstable diazonium salts which liberate Nitrogen gas ($N_2$) and form Alcohols.

$$ R-NH_2 + HNO_2 \xrightarrow{0-5^\circ C} [R-N_2^+Cl^-] \xrightarrow{H_2O} R-OH + N_2 \uparrow + HCl $$
This quantitative evolution of Nitrogen is used in the Van Slyke method for estimating amino acids.

B. Aromatic Primary Amines (Aniline)

React at low temperature ($0-5^\circ C$) to form stable Benzene Diazonium Chloride. This process is called Diazotization.

$$ C_6H_5NH_2 + NaNO_2 + 2HCl \xrightarrow{273-278 K} C_6H_5N_2^+Cl^- + NaCl + 2H_2O $$
Stability: Aromatic diazonium salts are stable at low temperatures due to resonance. Aliphatic ones decompose immediately.

2. Reaction with Secondary ($2^\circ$) Amines

Libermann Nitroso Test

Both Aliphatic and Aromatic secondary amines react with $HNO_2$ to form N-Nitrosoamines, which separate as a Yellow Oily Liquid.

$$ R_2NH + HO-N=O \rightarrow \underset{\text{N-Nitrosoamine (Yellow Oil)}}{R_2N-N=O} + H_2O $$

Test Confirmation: Upon warming the yellow oil with phenol and conc. $H_2SO_4$, a green solution is obtained, which turns blue on adding alkali (Liebermann's Nitroso Reaction).

3. Reaction with Tertiary ($3^\circ$) Amines

Different Behavior

A. Aliphatic Tertiary Amines: They form soluble Trialkyl Ammonium Nitrite salts (Acid-Base reaction). No visible change or gas evolution initially.
$$ R_3N + HNO_2 \rightarrow [R_3NH]^+NO_2^- \text{ (Soluble salt)} $$
B. Aromatic Tertiary Amines (e.g., N,N-Dimethylaniline): Undergo Electrophilic Substitution. The Nitroso group ($NO^+$) attacks the para-position to form a green-colored compound.
$$ C_6H_5N(CH_3)_2 + HNO_2 \rightarrow \underset{\text{p-Nitroso-N,N-dimethylaniline (Green)}}{p\text{-}ON-C_6H_4-N(CH_3)_2} + H_2O $$

4. Summary of Identification

Amine Type Reaction with $HNO_2$ Observation
$1^\circ$ Aliphatic Forms Alcohol + $N_2$ Brisk effervescence of $N_2$ gas.
$1^\circ$ Aromatic Forms Diazonium Salt Clear solution (at $0-5^\circ C$); Dye test positive.
$2^\circ$ (Both) Forms N-Nitrosoamine Yellow Oily Layer.
$3^\circ$ Aliphatic Forms Nitrite Salt Clear Solution (Soluble).
$3^\circ$ Aromatic Electrophilic Substitution Green colored solid/solution.

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