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NCERT Exemplar · Q34

Q.Explain why does colour of KMnO4KMnO_4 disappear when oxalic acid is added to its solution in acidic medium.

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The purple colour of KMnO4\text{KMnO}_4 disappears because MnO4−\text{MnO}_4^- (Mn in +7 oxidation state) is reduced to colourless Mn2+\text{Mn}^{2+} by oxalic acid in acidic medium — the reaction is a classic redox titration where the deep purple permanganate ion acts as a self-indicator.

Why This Happens: The Core Idea

The colour of KMnO4\text{KMnO}_4 comes from the permanganate ion, MnO4−\text{MnO}_4^-, where manganese is in its highest oxidation state, +7. This ion absorbs light in the visible region (green-yellow) due to charge transfer transitions, giving the solution its characteristic deep purple colour.

When you add oxalic acid (H2C2O4\text{H}_2\text{C}_2\text{O}_4) in acidic medium, a redox reaction occurs. The permanganate ion is a powerful oxidising agent, and oxalic acid is a reducing agent. The Mn in MnO4−\text{MnO}_4^- gets reduced from +7 to +2, forming the nearly colourless Mn2+\text{Mn}^{2+} ion. The oxalic acid gets oxidised to carbon dioxide and water.

The key point: the product Mn2+\text{Mn}^{2+} does not absorb visible light strongly — it appears pale pink only in very concentrated solutions, but in typical lab conditions it looks colourless. So as the reaction proceeds, the purple colour fades and eventually disappears completely.

Watch out

A common mistake is to think the colour disappears because permanganate "reacts" without specifying the change in oxidation state. The colour change is directly linked to the change in electronic structure of Mn — from MnO4−\text{MnO}_4^- (d⁰, intense charge transfer) to Mn2+\text{Mn}^{2+} (d⁵, weak d-d transitions). It is not simply "dilution" or "neutralisation".

Step-by-Step Breakdown

  1. Identify the species and their roles

    In acidic medium, KMnO4\text{KMnO}_4 dissociates to give K+\text{K}^+ and MnO4−\text{MnO}_4^-. Oxalic acid exists mostly as H2C2O4\text{H}_2\text{C}_2\text{O}_4 (or its conjugate base HC2O4−\text{HC}_2\text{O}_4^- depending on pH). The medium is acidified, typically with dilute H2SO4\text{H}_2\text{SO}_4, to provide H+\text{H}^+ ions.

  2. Write the half-reactions

    The reduction half-reaction for permanganate in acidic medium is:

MnO4−+8H++5e−→Mn2++4H2O\text{MnO}_4^- + 8\text{H}^+ + 5e^- \rightarrow \text{Mn}^{2+} + 4\text{H}_2\text{O}

The oxidation half-reaction for oxalic acid is:

H2C2O4→2CO2+2H++2e−\text{H}_2\text{C}_2\text{O}_4 \rightarrow 2\text{CO}_2 + 2\text{H}^+ + 2e^-

  1. Balance the overall redox equation To balance electrons, multiply the reduction half by 2 and the oxidation half by 5:

2MnO4−+16H++10e−→2Mn2++8H2O2\text{MnO}_4^- + 16\text{H}^+ + 10e^- \rightarrow 2\text{Mn}^{2+} + 8\text{H}_2\text{O}

5H2C2O4→10CO2+10H++10e−5\text{H}_2\text{C}_2\text{O}_4 \rightarrow 10\text{CO}_2 + 10\text{H}^+ + 10e^-

Adding them gives:

2MnO4−+5H2C2O4+6H+→2Mn2++10CO2+8H2O2\text{MnO}_4^- + 5\text{H}_2\text{C}_2\text{O}_4 + 6\text{H}^+ \rightarrow 2\text{Mn}^{2+} + 10\text{CO}_2 + 8\text{H}_2\text{O}

2MnO4−+5H2C2O4+6H+→2Mn2++10CO2+8H2O2\text{MnO}_4^- + 5\text{H}_2\text{C}_2\text{O}_4 + 6\text{H}^+ \rightarrow 2\text{Mn}^{2+} + 10\text{CO}_2 + 8\text{H}_2\text{O}

  1. Track the colour change …

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