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Problems · Problem 7.5

Q.Which of the following species, do not show disproportionation reaction and why ? ClO–, ClO2–, ClO3– and ClO4– Also write reaction for each of the species that disproportionates.

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Only ClO₄⁻ does not disproportionate — chlorine there is already at its highest possible oxidation state (+7), with no room to oxidise further. ClO⁻, ClO₂⁻, and ClO₃⁻ all disproportionate, since chlorine sits at an intermediate state (+1, +3, and +5 respectively) in each of them.

Understanding Disproportionation

Disproportionation is a special type of redox reaction where the same element in a single species undergoes both oxidation and reduction simultaneously. For this to happen, the element must be in an intermediate oxidation state—it needs room to both increase (oxidise) and decrease (reduce) its oxidation number.

The key question: can chlorine in each oxyanion move both up and down the oxidation ladder?

Chlorine's oxidation states in these species are:

  • ClO⁻: Cl is +1
  • ClO₂⁻: Cl is +3
  • ClO₃⁻: Cl is +5
  • ClO₄⁻: Cl is +7

Chlorine's range spans from -1 (in Cl⁻) to +7 (its maximum). Any species where chlorine sits at an intermediate value can potentially disproportionate. But if chlorine is already at or near its maximum oxidation state, it has nowhere to go upward—disproportionation becomes impossible.

Tip

A quick rule: species with the element in its highest oxidation state cannot disproportionate because oxidation (going higher) is blocked. Similarly, the lowest state cannot disproportionate because reduction is blocked.

Analysis of Each Species

1. ClO⁻ (hypochlorite, Cl in +1 state)

Chlorine at +1 is well within the intermediate range. It can:

  • Reduce to Cl⁻ (oxidation state -1)
  • Oxidise to ClO₃⁻ (oxidation state +5)

This species does disproportionate in alkaline solution:

3ClO−⟶2Cl−+ClO3−3\text{ClO}^- \longrightarrow 2\text{Cl}^- + \text{ClO}_3^-

Here, two chlorine atoms reduce from +1 to -1, while one oxidises from +1 to +5.


2. ClO₂⁻ (chlorite, Cl in +3 state)

Chlorine at +3 is also intermediate. It can:

  • Reduce to Cl⁻ (oxidation state -1)
  • Oxidise to ClO₃⁻ (oxidation state +5)

This species does disproportionate:

6ClO2−→hν4ClO3−+2Cl−6\text{ClO}_2^- \xrightarrow{h\nu} 4\text{ClO}_3^- + 2\text{Cl}^-

This disproportionation is photochemical — it happens on absorbing light (hνh\nu). Four chlorine atoms are oxidised from +3 to +5, while two are reduced from +3 to -1.


3. ClO₃⁻ (chlorate, Cl in +5 state)

Chlorine at +5 is still an intermediate state — the next higher state, +7 (ClO₄⁻), is reachable, and so are lower states such as -1 (Cl⁻). This species does disproportionate:

4ClO3−⟶Cl−+3ClO4−4\text{ClO}_3^- \longrightarrow \text{Cl}^- + 3\text{ClO}_4^-

One chlorine atom is reduced all the way from +5 to -1, while the other three are each oxidised from +5 to +7.


4. ClO₄⁻ (perchlorate, Cl in +7 state)

Chlorine at +7 is at its maximum oxidation state. It cannot oxidise further—there's no +8 or +9 for chlorine, so there is no higher state left for it to disproportionate into. Therefore, disproportionation is impossible.

ClO₄⁻ is the only one of the four that does not disproportionate.

Watch out

A common mistake is thinking that any oxyanion can disproportionate. Remember: the element must have accessible oxidation states both above and below its current value. Maximum and minimum states are dead ends.

Summary Table

SpeciesOxidation State of ClDisproportionates?Reason
ClO⁻+1YesIntermediate state; can go to -1 and +5
ClO₂⁻+3YesIntermediate state; can go to -1 and +5
ClO₃⁻+5YesIntermediate state; can go to -1 and +7
ClO₄⁻+7NoMaximum oxidation state; cannot oxidise further
✓Final answer

Only ClO₄⁻ does not disproportionate, because chlorine is already at its maximum oxidation state (+7). ClO⁻, ClO₂⁻, and ClO₃⁻ all disproportionate:

  • 3ClO−⟶2Cl−+ClO3−3\text{ClO}^- \longrightarrow 2\text{Cl}^- + \text{ClO}_3^-
  • 6ClO2−→hν4ClO3−+2Cl−6\text{ClO}_2^- \xrightarrow{h\nu} 4\text{ClO}_3^- + 2\text{Cl}^-
  • 4ClO3−⟶Cl−+3ClO4−4\text{ClO}_3^- \longrightarrow \text{Cl}^- + 3\text{ClO}_4^-

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