What is the order of relative basic strength of $\mathrm{ClO}_2^{-}, \mathrm{ClO}_3^{-}, \mathrm{ClO}_4^{-} ?$

What is the order of relative basic strength of $\mathrm{ClO}_2^{-}, \mathrm{ClO}_3^{-}, \mathrm{ClO}_4^{-} ?$
  1. $\mathrm{ClO}_2^{-}>\mathrm{ClO}_3^{-}>\mathrm{ClO}_4^{-}$
  2. $\mathrm{ClO}_3^{-}>\mathrm{ClO}_2^{-}>\mathrm{ClO}_4^{-}$
  3. $\mathrm{ClO}_4^{-}>\mathrm{ClO}_2^{-}>\mathrm{ClO}_3^{-}$
  4. $\mathrm{ClO}_2^{-}>\mathrm{ClO}_4^{-}>\mathrm{ClO}_3^{-}$

Solution

More be the oxidation state of central atom (i.e. $\mathrm{Cl}$-atom), more is the acidic nature of the species and lesser will be the basic strength. As, oxidation number of : $\begin{aligned} \mathrm{Cl} \text { in } \mathrm{ClO}_2^{-} \rightarrow x-4 & =-1 \\ x & =+3 \\ \mathrm{Cl} \mathrm{in} \mathrm{ClO}_3^{-} \rightarrow x-6 & =-1 \\ x & =+5 \\ \mathrm{C} \mathrm{lin} \mathrm{ClO}_4^{-} \rightarrow x-8 & =-1 \\ x & =+7\end{aligned}$ Thus, order of acidic nature is $\mathrm{ClO}_4^{-}>\mathrm{ClO}_3^{-}>\mathrm{ClO}_2^{-}$ and order for basic strength is $\mathrm{ClO}_2^{-}>\mathrm{ClO}_3^{-}>\mathrm{ClO}_4^{-}$. Alternate method The more be the oxygen atom in the given species, the more is the dispersion of electrons from Cl-atoms, which decreases the basic strength. $\because \mathrm{ClO}_2^{-}$has only two oxygen atoms while $\mathrm{ClO}_4^{-}$has four oxygen atoms. Thus, order of basic strength is $\mathrm{ClO}_2^{-}>\mathrm{ClO}_3^{-}>\mathrm{ClO}_4^{-}$ Hence, option (a) is the correct answer.

Asked in: TEST SERIES MHT-CET Full Test 6

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