Basicity of Amines

01Basicity of Amines

Amines as bases

This section covers how amines behave as weak Brønsted–Lowry bases by using the nitrogen lone pair to accept a proton.

The nitrogen lone pair

Amines are weak bases. The nitrogen atom carries a lone pair of electrons that can form a dative covalent bond with a proton. An amine can therefore act as a Brønsted–Lowry proton acceptor.

Methylamine establishes the following equilibrium in water:

CHX3NHX2+HX2OCHX3NHX3X++OHX\ce{CH3NH2 + H2O <=> CH3NH3+ + OH-}

Only a low concentration of hydroxide ions is produced, so methylamine behaves as a weak base.

Reaction with acids

Amines accept protons from acids and form ammonium salts. For example, methylamine reacts with hydrochloric acid to produce methylammonium chloride:

CHX3NHX2+HClCHX3NHX3X++ClX\ce{CH3NH2 + HCl -> CH3NH3+ + Cl-}

For a primary amine, the proton-transfer step can be represented generally as:

RNHX2+HX+RNHX3X+\ce{RNH2 + H+ -> RNH3+}

Before protonation

The amine contains an available lone pair on the nitrogen atom.

Methylamine is CHX3NHX2\ce{CH3NH2}.

After protonation

The nitrogen has accepted HX+\ce{H+} and the resulting ammonium ion carries a positive charge.

CHX3NHX3X+\ce{CH3NH3+}

Amine salts are ionic compounds. Those containing small alkyl groups are water-soluble, with solubility decreasing as the hydrocarbon chain becomes longer.

Phenylamine is only slightly soluble in water, whereas phenylammonium chloride is soluble. Treatment of an amine salt with sodium hydroxide converts it back into the amine.

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