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Electrochemistry question

2021 · 24 Feb · Shift 2 · Q21
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Electrochemistry question

2021 · 24 Feb · Shift 2 · Q21

JEE MainChemistryElectrochemistryNumerical+4 / −1
The magnitude of the change in oxidising power of the MnO4−/Mn2+MnO_4^ - /M{n^{2 + }}MnO4−​/Mn2+ couple is x ×\times× 10 −-− 4 V, if the H+H^+H+ concentration is decreased from 1M to 10 −-− 4 M at 25 ∘^\circ∘ C. (Assume concentration of MnO4−MnO_4^ -MnO4−​ and Mn2+M{n^{2 + }}Mn2+ to be same on change in H+H^+H+ concentration). The value of x is ‾\underline{\hspace{2cm}}​. [Given :2.303RTF=0.059]\left[ {Given\,:{{2.303RT} \over F} = 0.059} \right][Given:F2.303RT​=0.059]
Numerical answer
View written solutionFree

Correct answer: 3776

  1. Write the relevant reduction half-reaction

For the couple MnO4−/Mn2+MnO_4^- / Mn^{2+}MnO4−​/Mn2+ in acidic medium:

MnO4−+8H++5e−→Mn2++4H2OMnO_4^- + 8H^+ + 5e^- \rightarrow Mn^{2+} + 4H_2OMnO4−​+8H++5e−→Mn2++4H2​O

  1. Write the Nernst equation

For the reduction potential,

E=E∘−0.0595log⁡([Mn2+][MnO4−][H+]8)E = E^\circ - \frac{0.059}{5}\log\left(\frac{[Mn^{2+}]}{[MnO_4^-][H^+]^8}\right)E=E∘−50.059​log([MnO4−​][H+]8[Mn2+]​)

Given that the concentrations of MnO4−MnO_4^-MnO4−​ and Mn2+Mn^{2+}Mn2+ remain the same, only [H+][H^+][H+] changes. So the change in potential depends only on the [H+]8[H^+]^8[H+]8 term.

  1. Find the change in potential when [H+][H^+][H+] changes

Initially,

[H+]1=1 M[H^+]_1 = 1\,M[H+]1​=1M

Finally,

[H+]2=10−4 M[H^+]_2 = 10^{-4}\,M[H+]2​=10−4M

Using the Nernst equation, the change in reduction potential is:

ΔE=E2−E1\Delta E = E_2 - E_1ΔE=E2​−E1​

Since only [H+][H^+][H+] changes,

E=E∘−0.0595log⁡(constant[H+]8)E = E^\circ - \frac{0.059}{5}\log\left(\frac{\text{constant}}{[H^+]^8}\right)E=E∘−50.059​log([H+]8constant​)

This can be written as

E=constant+0.0595⋅8log⁡[H+]E = \text{constant} + \frac{0.059}{5}\cdot 8\log[H^+]E=constant+50.059​⋅8log[H+]

Hence,

ΔE=8×0.0595(log⁡[H+]2−log⁡[H+]1)\Delta E = \frac{8\times 0.059}{5}\left(\log[H^+]_2 - \log[H^+]_1\right)ΔE=58×0.059​(log[H+]2​−log[H+]1​)

Now,

log⁡(10−4)=−4,log⁡(1)=0\log(10^{-4}) = -4, \quad \log(1)=0log(10−4)=−4,log(1)=0

So,

ΔE=8×0.0595(−4)\Delta E = \frac{8\times 0.059}{5}(-4)ΔE=58×0.059​(−4)

ΔE=−1.8885\Delta E = -\frac{1.888}{5}ΔE=−51.888​

ΔE=−0.3776 V\Delta E = -0.3776\,VΔE=−0.3776V

Thus, the magnitude of change in oxidising power is

∣ΔE∣=0.3776 V|\Delta E| = 0.3776\,V∣ΔE∣=0.3776V

  1. Match with the given form

The question states magnitude =x×10−4 V= x \times 10^{-4}\,V=x×10−4V.

So,

0.3776=x×10−40.3776 = x \times 10^{-4}0.3776=x×10−4

x=0.3776×104=3776x = 0.3776 \times 10^4 = 3776x=0.3776×104=3776

  1. Final answer

x=3776\boxed{x=3776}x=3776​

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