JEE MAIN - Chemistry (2025 - 28th January Morning Shift - No. 9)

Given below are two statements:

Statement I: In the oxalic acid vs $\mathrm{KMnO}_4$ (in the presence of dil $\mathrm{H}_2 \mathrm{SO}_4$ ) titration the solution needs to be heated initially to $60^{\circ} \mathrm{C}$, but no heating is required in Ferrous ammonium sulphate (FAS) vs $\mathrm{KMnO}_4$ titration (in the presence of dil $\mathrm{H}_2 \mathrm{SO}_4$)

Statement II: In oxalic acid vs $\mathrm{KMnO}_4$ titration, the initial formation of $\mathrm{MnSO}_4$ takes place at high temperature, which then acts as catalyst for further reaction. In the case of FAS vs $\mathrm{KMnO}_4$, heating oxidizes $\mathrm{Fe}^{2+}$ into $\mathrm{Fe}^{3+}$ by oxygen of air and error may be introduced in the experiment.

In the light of the above statements, choose the correct answer from the options given below

Statement I is false but Statement II is true
Statement I is true but Statement II is false
Both Statement I and Statement II are true
Both Statement I and Statement II are false

Explanation

For the titration: Oxalic acid v/s $\mathrm{KMnO}_4$

$$\begin{aligned} & 2 \mathrm{MnO}_4^{-}+5(\mathrm{COO})_2^{2-}+16 \mathrm{H}^{+} \rightarrow \\ & 10 \mathrm{CO}_2+2 \mathrm{Mn}^{2+}+8 \mathrm{H}_2 \mathrm{O} \end{aligned}$$

This reaction is slow at room temperature, but becomes fast at $60^{\circ} \mathrm{C}$. Manganese(II) ions catalyse the reaction; thus, the reaction is autocatalytic; once manganese(II) ions are formed, it becomes faster and faster.

The titration of FAS v/s $\mathrm{KMnO}_4$ do not require heating because at higher temperature the oxidation of $\mathrm{Fe}^{+2}$ to $\mathrm{Fe}^{+3}$ by atmospheric $\mathrm{O}_2$ will be prominent.

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