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Electrochemistry question

2022 · 28 Jun · Shift 2 · Q15
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Electrochemistry question

2022 · 28 Jun · Shift 2 · Q15

JEE MainChemistryElectrochemistryNumerical+4 / −1
For the given reactions Sn2+Sn^{2+}Sn2+ + 2e −→-\to−→ Sn Sn4+Sn^{4+}Sn4+ + 4e −→-\to−→ Sn the electrode potentials are ; ESn2+/Sno=−0.140E_{S{n^{2 + }}/Sn}^o = - 0.140ESn2+/Sno​=−0.140 V and ESn4+/Sno=+0.010E_{S{n^{4 + }}/Sn}^o = + 0.010ESn4+/Sno​=+0.010 V. The magnitude of standard electrode potential for Sn4+/Sn2+S{n^{4 + }}/S{n^{2 + }}Sn4+/Sn2+ i.e. ESn4+/Sn2+oE_{S{n^{4 + }}/S{n^{2 + }}}^oESn4+/Sn2+o​ is ‾\underline{\hspace{2cm}}​×\times× 10 −-− 2 V. (Nearest integer)
Numerical answer
View written solutionFree

Correct answer: 16

  1. We are given the standard reduction potentials:

Sn2++2e−→Sn,E1∘=−0.140 VSn^{2+} + 2e^- \to Sn, \qquad E_1^\circ = -0.140\,\text{V}Sn2++2e−→Sn,E1∘​=−0.140V

Sn4++4e−→Sn,E2∘=+0.010 VSn^{4+} + 4e^- \to Sn, \qquad E_2^\circ = +0.010\,\text{V}Sn4++4e−→Sn,E2∘​=+0.010V

We need to find:

Sn4++2e−→Sn2+,ESn4+/Sn2+∘=?Sn^{4+} + 2e^- \to Sn^{2+}, \qquad E^\circ_{Sn^{4+}/Sn^{2+}} = ?Sn4++2e−→Sn2+,ESn4+/Sn2+∘​=?

  1. Standard electrode potentials cannot be added directly, so we use the relation with standard Gibbs free energy:

ΔG∘=−nFE∘\Delta G^\circ = -nFE^\circΔG∘=−nFE∘

  1. Write the target reaction as a combination of the given reactions.

Reaction (A): Sn2++2e−→Sn(EA∘=−0.140 V)Sn^{2+} + 2e^- \to Sn \qquad (E_A^\circ = -0.140\,\text{V})Sn2++2e−→Sn(EA∘​=−0.140V)

Reverse it: Sn→Sn2++2e−Sn \to Sn^{2+} + 2e^-Sn→Sn2++2e− Then ΔGA∘,rev=−ΔGA∘\Delta G_A^{\circ,\text{rev}} = -\Delta G_A^\circΔGA∘,rev​=−ΔGA∘​

Reaction (B): Sn4++4e−→Sn(EB∘=+0.010 V)Sn^{4+} + 4e^- \to Sn \qquad (E_B^\circ = +0.010\,\text{V})Sn4++4e−→Sn(EB∘​=+0.010V)

Add reaction (B) to reverse of (A) multiplied suitably:

Actually, Sn4++4e−→SnSn^{4+} + 4e^- \to SnSn4++4e−→Sn Sn→Sn2++2e−Sn \to Sn^{2+} + 2e^-Sn→Sn2++2e−

Sn4++2e−→Sn2+Sn^{4+} + 2e^- \to Sn^{2+}Sn4++2e−→Sn2+

So Gibbs energies add:

  1. Compute ΔG∘\Delta G^\circΔG∘ values.

For reaction (B): ΔGB∘=−nFEB∘=−4F(0.010)=−0.040F\Delta G_B^\circ = -nFE_B^\circ = -4F(0.010) = -0.040FΔGB∘​=−nFEB∘​=−4F(0.010)=−0.040F

For reaction (A): ΔGA∘=−2F(−0.140)=+0.280F\Delta G_A^\circ = -2F(-0.140) = +0.280FΔGA∘​=−2F(−0.140)=+0.280F

So for reverse of (A): ΔGA∘,rev=−0.280F\Delta G_A^{\circ,\text{rev}} = -0.280FΔGA∘,rev​=−0.280F

Hence for Sn4++2e−→Sn2+Sn^{4+} + 2e^- \to Sn^{2+}Sn4++2e−→Sn2+

ΔG∘=ΔGB∘+ΔGA∘,rev\Delta G^\circ = \Delta G_B^\circ + \Delta G_A^{\circ,\text{rev}}ΔG∘=ΔGB∘​+ΔGA∘,rev​ =−0.040F+(−0.280F)= -0.040F + (-0.280F)=−0.040F+(−0.280F) =−0.320F= -0.320F=−0.320F

  1. Now convert back to electrode potential for the 2-electron reaction:

ΔG∘=−nFE∘\Delta G^\circ = -nFE^\circΔG∘=−nFE∘ −0.320F=−2FE∘-0.320F = -2F E^\circ−0.320F=−2FE∘

E∘=0.3202=0.160 VE^\circ = \frac{0.320}{2} = 0.160\,\text{V}E∘=20.320​=0.160V

  1. The question asks for the magnitude in the form:

‾×10−2 V\underline{\hspace{2cm}} \times 10^{-2}\,\text{V}​×10−2V

Since 0.160 V=16×10−2 V0.160\,\text{V} = 16 \times 10^{-2}\,\text{V}0.160V=16×10−2V

So the required nearest integer is:

16\boxed{16}16​

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