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JEE Advanced levelSingle correct optionDifficulty 3 of 3g2214

Methylamine and trimethylamine have gas-phase proton affinities of 899 and 942 kJ/mol respectively, so trimethylamine is the stronger base in the gas phase. In water the pKa values of the conjugate acids are 10.6 for and 9.8 for . The reversal in water is mainly because

  1. A has only one for hydrogen bonding to water, so it loses more solvation stabilisation than
  2. Btrimethylamine has no lone pair in water
  3. Cthe effect of methyl groups switches to in water
  4. Dwater is a stronger acid than the trimethylammonium ion

Answer: A

In the gas phase the electron-releasing and polarisable methyl groups stabilise the ammonium ion, so more methyl groups mean greater basicity. In water, the ammonium ions are stabilised by hydrogen bonds from their bonds. has three, only one, so the loss of solvation outweighs the inductive gain and trimethylamine is the weaker base in water.
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