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:
- +I Effect: Increases basicity as the number of methyl groups increases (3∘>2∘>1∘).
- Solvation Effect: Decreases basicity as the number of methyl groups increases due to reduced hydrogen bonding (1∘>2∘>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), the strongest base. Methylamine (CH3NH2) is stronger than trimethylamine ((CH3)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.