10.22 Why are lithium salts commonly hydrated and those of the other alkali ions usually anhydrous?

Answers (1)
R Rakesh

Lithium-ion is the smallest among the other alkali metal ions. Hence it has higher polarising power than others and so it can polarise water molecule more easily than other alkali metals. Hence the water molecules are more attracted towards Li salts as the water of crystallisation. Li+ has a maximum degree of hydration and for this reason, lithium salts are mostly hydrated, e.g., LiCl· 2H2O 

As the down the group size of ions increase, their polarising power decreases. Hence other alkali metal ions usually form anhydrous salts.