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NEET CHEMISTRYMedium

What is the correct order of the methyl-substituted amines' basic strength in an aqueous solution?

A

CH3NH2>(CH3)2NH>(CH3)3NCH_3NH_2 > (CH_3)_2NH > (CH_3)_3N

B

(CH3)2NH>CH3NH2>(CH3)3N(CH_3)_2NH > CH_3NH_2 > (CH_3)_3N

C

(CH3)3N>CH3NH2>(CH3)2NH(CH_3)_3N > CH_3NH_2 > (CH_3)_2NH

D

(CH3)2NH>(CH3)3N>CH3NH2(CH_3)_2NH > (CH_3)_3N > CH_3NH_2

Step-by-Step Solution

The basic strength of aliphatic amines in an aqueous solution is governed by a combination of factors: the +I (inductive) effect of the alkyl groups, the extent of hydrogen bonding (solvation) of the protonated amine, and steric hindrance.

For methyl-substituted amines:

  1. +I Effect: Increases basicity as the number of methyl groups increases (3>2>13^\circ > 2^\circ > 1^\circ).
  2. Solvation Effect: Decreases basicity as the number of methyl groups increases due to reduced hydrogen bonding (1>2>31^\circ > 2^\circ > 3^\circ).
  3. Steric Hindrance: Bulky methyl groups hinder the approach of the proton and the solvent molecules.

The combined effect makes the secondary amine, dimethylamine ((CH3)2NH(CH_3)_2NH), the strongest base. Methylamine (CH3NH2CH_3NH_2) is stronger than trimethylamine ((CH3)3N(CH_3)_3N) because the steric hindrance and poor solvation of the tertiary ammonium ion outweigh the +I effect. Therefore, the correct order is (CH3)2NH>CH3NH2>(CH3)3N(CH_3)_2NH > CH_3NH_2 > (CH_3)_3N.

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