Saturday 29 April 2017

The reaction of phenylamine with water,Why is phenylamine such a weak base?



The reaction of phenylamine with water

This is where it is possible to tell that phenylamine is a much weaker base than ammonia and the aliphatic amines like methylamine and ethylamine.
Phenylamine reacts reversibly with water to give phenylammonium ions and hydroxide ions.
The position of equilibrium lies well to the left of the corresponding ammonia or aliphatic amine equilibria - which means that not many hydroxide ions are formed in the solution.
The effect of this is that the pH of a solution of phenylamine will be quite a bit lower than a solution of ammonia or one of the aliphatic amines of the same concentration. For example, a 0.1 M phenylamine solution has a pH of about 9 compared to a pH of about 11 for 0.1 M ammonia solution.


Why is phenylamine such a weak base?
Amines are bases because they pick up hydrogen ions on the lone pair on the nitrogen atom. In phenylamine, the attractiveness of the lone pair is lessened because of the way it interacts with the ring electrons.
The lone pair on the nitrogen touches the delocalised ring electrons . . .

. . . and becomes delocalised with them:

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