JEE MAIN - Chemistry (2024 - 8th April Morning Shift - No. 2)
Thiosulphate reacts differently with iodine and bromine in the reactions given below:
$$\begin{aligned} & 2 \mathrm{~S}_2 \mathrm{O}_3^{2-}+\mathrm{I}_2 \rightarrow \mathrm{S}_4 \mathrm{O}_6^{2-}+2 \mathrm{I}^{-} \\ & \mathrm{S}_2 \mathrm{O}_3^{2-}+5 \mathrm{Br}_2+5 \mathrm{H}_2 \mathrm{O} \rightarrow 2 \mathrm{SO}_4^{2-}+4 \mathrm{Br}^{-}+10 \mathrm{H}^{+} \end{aligned}$$
Which of the following statement justifies the above dual behaviour of thiosulphate?
Explanation
In the given reactions:
$$\begin{aligned} & 2 \mathrm{S}_2\mathrm{O}_3^{2-} + \mathrm{I}_2 \rightarrow \mathrm{S}_4\mathrm{O}_6^{2-} + 2 \mathrm{I}^{-} \\\\ & \mathrm{S}_2\mathrm{O}_3^{2-} + 5 \mathrm{Br}_2 + 5 \mathrm{H}_2\mathrm{O} \rightarrow 2 \mathrm{SO}_4^{2-} + 4 \mathrm{Br}^{-} + 10 \mathrm{H}^{+} \end{aligned}$$
In the first reaction with iodine ($I_2$), thiosulfate ($S_2O_3^{2-}$) acts as a reducing agent, converting $I_2$ to $I^{-}$, while it is itself oxidized to $S_4O_6^{2-}$. This indicates that iodine is acting as an oxidant (oxidizing agent), getting reduced in the process.
In the second reaction with bromine ($Br_2$), thiosulfate is oxidized more extensively, being converted all the way to sulfate ($SO_4^{2-}$), with hydrogen ions ($H^+$) and bromide ions ($Br^-$) also produced. This shows that bromine acts as a stronger oxidant compared to iodine, as it promotes a complete oxidation of $S_2O_3^{2-}$ to $SO_4^{2-}$.
Given these observations, the correct option that justifies the dual behavior of thiosulfate reacting with iodine and bromine differently is:
Option C: Bromine is a stronger oxidant than iodine
This statement correctly explains why thiosulfate is oxidized to $S_4O_6^{2-}$ in the presence of iodine, and to $SO_4^{2-}$ in the presence of bromine. Bromine's stronger oxidizing ability leads to a more complete oxidation of thiosulfate compared to the oxidation by iodine.
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