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Q.The product of the oxidation of I−I^{-} with MnO4−MnO_4^{-} in alkaline medium is : (A) IO4−IO_4^{-} (B) I2I_2 (C) IO−IO^{-} (D) IO3−IO_3^{-}

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In alkaline medium, permanganate (MnO4−MnO_4^-) oxidises iodide (I−I^-) to iodate (IO3−IO_3^-), not to iodine or periodate. The balanced reaction shows I−I^- loses 6 electrons to form IO3−IO_3^-, while MnO4−MnO_4^- gains 3 electrons to form MnO2MnO_2. The correct product is IO3−IO_3^-, option (D).

Why the medium matters

The oxidation state of iodine in its products depends heavily on the pH of the solution. Permanganate is a powerful oxidising agent, but its reduction product changes with medium:

  • In acidic medium: MnO4−→Mn2+MnO_4^- \rightarrow Mn^{2+} (gains 5 electrons)
  • In neutral/alkaline medium: MnO4−→MnO2MnO_4^- \rightarrow MnO_2 (gains 3 electrons)

This difference in electron gain per mole of permanganate directly affects how far it can oxidise iodide. In alkaline medium, permanganate is a milder oxidising agent (gains only 3 electrons) compared to acidic medium (gains 5 electrons). Yet it still oxidises I−I^- all the way to IO3−IO_3^-, not stopping at I2I_2.

Step-by-step reasoning

  1. Identify the half-reactions

    Iodide (I−I^-) has oxidation state −1-1. The possible products given are:

    • IO4−IO_4^-: iodine in +7+7 state
    • I2I_2: iodine in 00 state
    • IO−IO^-: iodine in +1+1 state (hypoiodite)
    • IO3−IO_3^-: iodine in +5+5 state (iodate)

    In alkaline medium, permanganate reduces to MnO2MnO_2 (manganese in +4+4 state, from +7+7 in MnO4−MnO_4^-).

  2. Balance the oxidation half-reaction

    Iodide going to iodate:

I−→IO3−I^- \rightarrow IO_3^-

Balance oxygen with water (alkaline medium):

I−+3H2O→IO3−+6H+I^- + 3H_2O \rightarrow IO_3^- + 6H^+

Balance charge: left side has −1-1, right side has −1+6=+5-1 + 6 = +5. Add 6 electrons to right:

I−+3H2O→IO3−+6H++6e−I^- + 3H_2O \rightarrow IO_3^- + 6H^+ + 6e^-

In alkaline medium, add OH−OH^- to neutralise H+H^+:

I−+6OH−→IO3−+3H2O+6e−I^- + 6OH^- \rightarrow IO_3^- + 3H_2O + 6e^-

So each I−I^- loses 6 electrons to become IO3−IO_3^-.

  1. Balance the reduction half-reaction

    Permanganate to manganese dioxide in alkaline medium:

MnO4−→MnO2MnO_4^- \rightarrow MnO_2

Balance oxygen with water:

MnO4−+2H2O→MnO2+4OH−MnO_4^- + 2H_2O \rightarrow MnO_2 + 4OH^-

Balance charge: left −1-1, right −4-4. Add 3 electrons to left:

MnO4−+2H2O+3e−→MnO2+4OH−MnO_4^- + 2H_2O + 3e^- \rightarrow MnO_2 + 4OH^-

So each MnO4−MnO_4^- gains 3 electrons.

  1. Combine the half-reactions

    To equalise electrons: multiply reduction half by 2 (gives 6 electrons gained) and oxidation half by 1 (gives 6 electrons lost):

2MnO4−+4H2O+6e−→2MnO2+8OH−2MnO_4^- + 4H_2O + 6e^- \rightarrow 2MnO_2 + 8OH^-

I−+6OH−→IO3−+3H2O+6e−I^- + 6OH^- \rightarrow IO_3^- + 3H_2O + 6e^-

Adding:

2MnO4−+I−+4H2O+6OH−→2MnO2+IO3−+3H2O+8OH−2MnO_4^- + I^- + 4H_2O + 6OH^- \rightarrow 2MnO_2 + IO_3^- + 3H_2O + 8OH^-

Cancel 3H2O3H_2O from both sides and 6OH−6OH^- from both sides: …

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