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On the other hand, in methylamine due to the +I effect of methyl group (CH3 gp is EDG), the
electron density on the N-atom is increased, hence more basic.
As a result, aniline is less basic than methylamine. Thus, pKb of aniline is more than that of
methylamine.
3. Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
Due to the +I effect of −CH3 group, methylamine is more basic than water. Therefore, methylamine
reacts with water to produce OH− ions by accepting H+ ions from water.
Ferric chloride (FeCl3) dissociates in water to form Fe3+ and Cl− ions.
Then, OH− ion reacts with Fe3+ ion to form a precipitate of hydrated ferric oxide.
6. Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
Aromatic diazonium salts are more stable because of resonance, there is dispersal of positive charge.
2
Since O is more electronegative than N, the R-O-is more stable than R-NH- ion. Hence, alcohols
are more acidic than amines of comparable molecular masses.
10. Primary amines have higher boiling point than tertiary amines.
In tertiary amine, there are no H−atoms, hence there is no intermolecular hydrogen bonding
whereas in primary amines, two hydrogen atoms are present and hence undergo extensive
intermolecular H−bonding. Hence, primary amines have higher boiling points than tertiary amines.
15. How can the activating effect of –NH2 group in amines be controlled? (or) Why does the
reactivity of NH2 get reduced in acetanilide?
This can be done by protecting the –NH2 group by acetylation. In acetanilide, the lone pair of es- on
nitrogen is involved in resonance with oxygen atom. Thus, N acquires positive charge which reduces
the activating effect of NH2 group.
EDG (CH3, -OCH3), increases the basic strength [increases the e- density on nitrogen].
EWG (NO2, halogen), decreases the basic strength [decreases the e- density on nitrogen]
(ii) In increasing order of basic strength: C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2
C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH
(iv) In decreasing order of basic strength in gas phase: C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3