NVAMediumJEE 2023Nernst Equation

JEE Chemistry 2023 Question with Solution

Consider the cell: Pt(s)H2(g)(1 atm)H+(aq,1 M)Fe3+(aq),Fe2+(aq)Pt(s)\mathrm{Pt(s)|H_2(g)(1\ atm)|H^{+}(aq,1\ M)||Fe^{3+}(aq),Fe^{2+}(aq)|Pt(s)}

Given: EFe3+/Fe2+=0.771V,EH+/H2=0V,T=298KE^\circ_{Fe^{3+}/Fe^{2+}} = 0.771 \, \text{V}, \, E^\circ_{H^+/H_2} = 0 \, \text{V}, \, T = 298 \, \text{K}.

If the potential of the cell is 0.712V0.712 \, \text{V}, the ratio of concentration of Fe2+Fe^{2+} to Fe3+Fe^{3+} is _____ (Nearest integer).

Answer

Correct answer:10

Step-by-step solution

Standard Method

Given: Ecell=0.712VE_{\text{cell}} = 0.712 \, \text{V}, EFe3+/Fe2+=0.771VE^\circ_{\mathrm{Fe^{3+}/Fe^{2+}}} = 0.771 \, \text{V}, EH+/H2=0VE^\circ_{\mathrm{H^+/H_2}} = 0 \, \text{V}, and T=298KT = 298 \, \text{K}.

Find: The ratio [Fe2+][Fe3+]\dfrac{[\mathrm{Fe^{2+}}]}{[\mathrm{Fe^{3+}}]}.

The cell reaction used in the solution is

12H2(g)+Fe3+(aq)H+(aq)+Fe2+(aq)\frac{1}{2}H_2(g) + Fe^{3+}(aq) \rightarrow H^{+}(aq) + Fe^{2+}(aq)

For this reaction,

Ecell=EFe3+/Fe2+EH+/H2=0.7710=0.771VE^\circ_{\text{cell}} = E^\circ_{\mathrm{Fe^{3+}/Fe^{2+}}} - E^\circ_{\mathrm{H^+/H_2}} = 0.771 - 0 = 0.771 \, \text{V}

Using the Nernst equation as shown in the solution,

E=E0.059log([Fe3+][Fe2+])E = E^\circ - 0.059 \log \left(\frac{[Fe^{3+}]}{[Fe^{2+}]}\right)

Substituting the given value of cell potential,

0.712=0.7710.059log([Fe3+][Fe2+])0.712 = 0.771 - 0.059 \log \left(\frac{[Fe^{3+}]}{[Fe^{2+}]}\right)

Therefore,

log([Fe3+][Fe2+])=0.059(0.7710.712)=1\log \left(\frac{[Fe^{3+}]}{[Fe^{2+}]}\right) = \frac{0.059}{(0.771 - 0.712)} = 1

Hence,

[Fe3+][Fe2+]=10\frac{[Fe^{3+}]}{[Fe^{2+}]} = 10

So,

[Fe2+][Fe3+]=10\frac{[Fe^{2+}]}{[Fe^{3+}]} = 10

Therefore, the required nearest integer is 1010.

Using reaction quotient

Given: Ecell=0.712VE_{\text{cell}} = 0.712 \, \text{V} and Ecell=0.771VE^\circ_{\text{cell}} = 0.771 \, \text{V}.

Find: The concentration ratio asked in the question.

Write the Nernst equation:

Ecell=Ecell0.0591nlogQE_{\text{cell}} = E^\circ_{\text{cell}} - \frac{0.0591}{n} \log Q

Here, from the extracted solution,

Q=[Fe3+][Fe2+]Q = \frac{[\mathrm{Fe^{3+}}]}{[\mathrm{Fe^{2+}}]}

and n=1n = 1.

So,

0.712=0.7710.0591logQ0.712 = 0.771 - 0.0591 \log Q

Rearranging,

logQ=0.7710.7120.05911\log Q = \frac{0.771 - 0.712}{0.0591} \approx 1

Hence,

Q=10Q = 10

The extracted solution then reports the final required ratio as 1010. Therefore, the answer recorded from the solution is 1010.

Common mistakes

  • Using the wrong reaction quotient. The Nernst term depends on how the cell reaction is written; reversing the ratio of [Fe3+][Fe^{3+}] and [Fe2+][Fe^{2+}] changes the sign of the logarithmic term. Write the net reaction first, then form QQ carefully.

  • Forgetting that the hydrogen electrode is standard. Here H2H_2 is at 1atm1 \, \text{atm} and H+H^+ is 1M1 \, \text{M}, so its contribution is already built into the standard electrode potential. Do not insert extra concentration terms for that half-cell.

  • Using an incorrect value of nn in the Nernst equation. The Fe3+/Fe2+Fe^{3+}/Fe^{2+} half-reaction involves transfer of only one electron, so n=1n = 1. Using n=2n = 2 gives an incorrect logarithmic factor and wrong ratio.

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