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JEE Chemistry 2025 Question with Solution

Electrode potential diagram showing FeO4^{2-} to Fe^{3+} with +2.0 V, Fe^{3+} to Fe^{2+} with 0.8 V, and Fe^{2+} to Fe^0 with -0.5 V along arrows.

In the above diagram, the standard electrode potentials are given in volts (over the arrow). The value of EFeO42/Fe2+E^\circ_{FeO_4^{2-}/Fe^{2+}} is:

  • A

    1.7V1.7 \, \text{V}

  • B

    1.2V1.2 \, \text{V}

  • C

    2.1V2.1 \, \text{V}

  • D

    1.4V1.4 \, \text{V}

Answer

Correct answer:A

Step-by-step solution

Standard Method

Given: The standard electrode potentials are E1=2.0VE_1^\circ = 2.0 \, \text{V} for FeO42Fe3+FeO_4^{2-} \to Fe^{3+} and E2=0.8VE_2^\circ = 0.8 \, \text{V} for Fe3+Fe2+Fe^{3+} \to Fe^{2+}.

Find: EFeO42/Fe2+E^\circ_{FeO_4^{2-}/Fe^{2+}}.

For combining electrode potentials, potentials are not added directly unless the electron transfer is the same. Use the relation

ΔG=nFE\Delta G^\circ = -nFE^\circ

and add Gibbs free energies.

From the diagram:

  • FeO42Fe3+FeO_4^{2-} \to Fe^{3+} involves change of oxidation state from +6+6 to +3+3, so n1=3n_1 = 3.
  • Fe3+Fe2+Fe^{3+} \to Fe^{2+} involves n2=1n_2 = 1.
  • Overall, FeO42Fe2+FeO_4^{2-} \to Fe^{2+} involves change from +6+6 to +2+2, so n=4n = 4.

Therefore,

nFE=n1FE1n2FE2-nF E^\circ = -n_1 F E_1^\circ - n_2 F E_2^\circ

so

4E=3(2.0)+1(0.8)4E^\circ = 3(2.0) + 1(0.8) 4E=6.84E^\circ = 6.8 E=6.84=1.7VE^\circ = \frac{6.8}{4} = 1.7 \, \text{V}

Therefore, the value of EFeO42/Fe2+E^\circ_{FeO_4^{2-}/Fe^{2+}} is 1.7V1.7 \, \text{V}. The correct option is A.

Why direct addition is wrong

Given: The stepwise potentials are 2.0V2.0 \, \text{V} and 0.8V0.8 \, \text{V}.

Find: The overall reduction potential from FeO42FeO_4^{2-} to Fe2+Fe^{2+}.

A common incorrect approach is to write

E=2.0+0.8=2.8VE^\circ = 2.0 + 0.8 = 2.8 \, \text{V}

but this is not valid because standard electrode potentials are intensive quantities. The correct additive quantity is ΔG\Delta G^\circ.

Using

ΔG=nFE\Delta G^\circ = -nFE^\circ

we write

ΔGoverall=ΔG1+ΔG2\Delta G^\circ_{overall} = \Delta G^\circ_1 + \Delta G^\circ_2 4FE=3F(2.0)1F(0.8)-4F E^\circ = -3F(2.0) - 1F(0.8) 4E=6.84E^\circ = 6.8 E=1.7VE^\circ = 1.7 \, \text{V}

Hence, the overall standard electrode potential is 1.7V1.7 \, \text{V}.

Common mistakes

  • Adding electrode potentials directly as 2.0+0.8=2.8V2.0 + 0.8 = 2.8 \, \text{V} is wrong because EE^\circ is not directly additive when the number of electrons differs. Add ΔG\Delta G^\circ values instead using ΔG=nFE\Delta G^\circ = -nFE^\circ.

  • Using the wrong electron counts is a conceptual error. For FeO42Fe3+FeO_4^{2-} \to Fe^{3+}, the iron oxidation state changes from +6+6 to +3+3, so 33 electrons are involved; for Fe3+Fe2+Fe^{3+} \to Fe^{2+}, only 11 electron is involved.

  • Including the Fe2+Fe0Fe^{2+} \to Fe^0 step with 0.5V-0.5 \, \text{V} is wrong because the question asks only for FeO42/Fe2+FeO_4^{2-}/Fe^{2+}. Do not extend the pathway beyond the required half-reaction.

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