Comment on each of the following observations:

(a) The mobilities of the alkali metal ions in aqueous solution are Li⁺ < Na⁺ < K⁺ < Rb⁺ < Cs⁺

(b) Lithium is the only alkali metal to form a nitride directly.

(c) (where M = Ca, Sr or Ba) is nearly constant.

(a) On moving down the alkali group, the ionic and atomic sizes of the metals increase. The given alkali metal ions can be arranged in the increasing order of their ionic sizes as:

Li^{+ + + + +}

Smaller the size of an ion, the more highly is it hydrated. Since Li⁺ is the smallest, it gets heavily hydrated in an aqueous solution. On the other hand, Cs⁺ is the largest and so it is the least hydrated. The given alkali metal ions can be arranged in the decreasing order of their hydrations as:

Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺

Greater the mass of a hydrated ion, the lower is its ionic mobility. Therefore, hydrated Li⁺ is the least mobile and hydrated Cs⁺ is the most mobile. Thus, the given alkali metal ions can be arranged in the increasing order of their mobilities as:

Li^{+ + + + +}

(b) Unlike the other elements of group 1, Li reacts directly with nitrogen to form lithium nitride. This is because Li⁺ is very small in size and so its size is the most compatible with the N^3– ion. Hence, the lattice energy released is very high. This energy also overcomes the high amount of energy required for the formation of the N^3–ion.

(c) Electrode potential (E°) of any M²⁺/M electrode depends upon three factors:

(i) Ionisation enthalpy

(ii) Enthalpy of hydration

(iii) Enthalpy of vaporisation

The combined effect of these factors is approximately the same for Ca, Sr, and Ba. Hence, their electrode potentials are nearly constant.

a) We know, smaller the size, higher is the hydration energy. Because a small ion can move faster.
The mobility of the alkali metal ions in aqueous solution are :
Li+ < Na+ < K+ < Rb+ <Cs+
Due to smaller the size of the ion, it is more highly hydrated and greater the hydration of the ion; lower is its ionic mobility. Since the extent of hydration decreases in order.
Li+ >Na+ >K+ > Rb+> Cs+
Therefore , ionic mobility increases in the reverse order.
e.g., Li+ < Na+ < K+ < Rb+ < Cs+

(b) because of its smaller in size and diagonal relationship with Mg form Nitride directly.
6Li + N2 ---->2Li3N

(c) E°for M2+ +2e--->M
where M = Ca, Sr, Ba is almost same because, E°of any M2+/M electrode depends upon there factors :(i) enthalpy of vaporization (ii) Ionization enthalpy (iii) enthalpy of hydration.since, the combined effect of these factors is almost the same for Ca,Sr and Ba, therefore, their electrode potential are nearly constant.