Lanthanide contraction refers to the gradual decrease in the ionic radius of the lanthanide series as the atomic number increases, caused by the poor shielding effect of the 4f-electrons. Two important consequences of lanthanide contraction are: 1. Decreasing ionic radii: As the atomic number increases from \( La^{3+} \) to \( Lu^{3+} \), the size of the ions decreases, leading to an increase in the effective nuclear charge experienced by the electrons. This results in a decrease in the ionic radii. 2. Similarity between the 3d and 4d/5d elements: The lanthanide contraction leads to similarities in the properties of the lanthanide elements and the d-block elements in the same period. For example, \( Zr \) (a 4d element) and \( Hf \) (a 5d element) have very similar ionic radii due to the lanthanide contraction.
Thus, the lanthanide contraction results in smaller ionic radii and increased similarities between the properties of lanthanides and d-block elements.
Write IUPAC names of the following compounds and classify them into primary, secondary and tertiary amines.
(i) (CH3 )2CHNH2 (ii) CH3 (CH2 )2NH2 (iii) CH3NHCH(CH3 )2
(iv) (CH3 )3CNH2 (v) C6H5NHCH3 (vi) (CH3CH2 )2NCH3 (vii) m–BrC6H4NH2
Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine
(ii) Secondary and tertiary amines
(iii) Ethylamine and aniline
(iv) Aniline and benzylamine
(v) Aniline and N-methylaniline
Account for the following:
(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv) Although amino group is o– and p– directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines. (vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
