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Electrochemistry question

2022 · 30 Jun · Shift 1 · Q4
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  5. /2022 · 30 Jun · Shift 1 · Q4

Electrochemistry question

2022 · 30 Jun · Shift 1 · Q4

JEE MainChemistryElectrochemistryMCQ+4 / −1
In which of the following half cells, electrochemical reaction is pH dependent?
  1. A
    Pt ∣ Fe3+, Fe2+Pt\,|\,F{e^{3 + }},\,F{e^{2 + }}Pt∣Fe3+,Fe2+
  2. B
    MnO4− ∣Mn2+MnO_4^ - \,|M{n^{2 + }}MnO4−​∣Mn2+
  3. C
    Ag ∣ AgCl ∣Cl−1Ag\,|\,AgCl\,|C{l^{ - 1}}Ag∣AgCl∣Cl−1
  4. D
    12F2 ∣F−{1 \over 2}{F_2}\,|{F^ - }21​F2​∣F−
View written solutionFree

Correct answer: B

  1. Criterion for pH dependence
    A half-cell reaction is pH dependent if its electrode potential depends on [H+][H^+][H+] (or pH). From the Nernst equation, this happens when H+H^+H+ or OH−OH^-OH− appears in the half-reaction.

  2. Check each half-cell

Option A: Pt ∣ Fe3+,Fe2+Pt\,|\,Fe^{3+},Fe^{2+}Pt∣Fe3+,Fe2+

The half-reaction is Fe3++e−→Fe2+Fe^{3+}+e^- \rightarrow Fe^{2+}Fe3++e−→Fe2+ Nernst equation: E=E∘−0.05911log⁡[Fe2+][Fe3+]E=E^\circ-\frac{0.0591}{1}\log\frac{[Fe^{2+}]}{[Fe^{3+}]}E=E∘−10.0591​log[Fe3+][Fe2+]​ No H+H^+H+ or OH−OH^-OH− appears.
So, this electrode is not pH dependent.

Option B: MnO4− ∣ Mn2+MnO_4^-\,|\,Mn^{2+}MnO4−​∣Mn2+

In acidic medium, the half-reaction is MnO4−+8H++5e−→Mn2++4H2OMnO_4^-+8H^+ +5e^- \rightarrow Mn^{2+}+4H_2OMnO4−​+8H++5e−→Mn2++4H2​O Nernst equation: E=E∘−0.05915log⁡[Mn2+][MnO4−][H+]8E=E^\circ-\frac{0.0591}{5}\log\frac{[Mn^{2+}]}{[MnO_4^-][H^+]^8}E=E∘−50.0591​log[MnO4−​][H+]8[Mn2+]​ Since [H+][H^+][H+] appears explicitly, the electrode potential depends on pH.
So, this electrode is pH dependent.

Option C: Ag ∣ AgCl ∣Cl−Ag\,|\,AgCl\,|Cl^-Ag∣AgCl∣Cl−

The half-reaction is AgCl(s)+e−→Ag(s)+Cl−AgCl(s)+e^- \rightarrow Ag(s)+Cl^-AgCl(s)+e−→Ag(s)+Cl− Nernst equation: E=E∘−0.0591log⁡[Cl−]E=E^\circ-0.0591\log[Cl^-]E=E∘−0.0591log[Cl−] No H+H^+H+ or OH−OH^-OH− appears.
So, this electrode is not pH dependent.

Option D: 12F2 ∣F−\frac12F_2\,|F^-21​F2​∣F−

The half-reaction is 12F2+e−→F−\frac12F_2+e^- \rightarrow F^-21​F2​+e−→F− Nernst equation: E=E∘−0.0591log⁡[F−](PF2)1/2E=E^\circ-0.0591\log\frac{[F^-]}{(P_{F_2})^{1/2}}E=E∘−0.0591log(PF2​​)1/2[F−]​ No H+H^+H+ or OH−OH^-OH− appears.
So, this electrode is not pH dependent.

  1. Conclusion
    Only Option B has H+H^+H+ in the half-cell reaction, so only this half-cell is pH dependent.

B\boxed{\text{B}}B​

  1. Comparison with stored answer
    Stored correct answer: B
    Our derived answer: B
    So they agree.
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